Triazine ring-containing polymer and film forming composition containing same

ABSTRACT

For example, a triazine ring-containing polymer containing a repeating unit structure represented by Formula (24) below, 
     
       
         
         
             
             
         
       
         
         
           
             wherein R 102  represents a crosslinking group.

TECHNICAL FIELD

The present invention relates to a triazine ring-containing polymer anda film forming composition containing the same.

BACKGROUND ART

In recent years, there have been demands for highly functional polymermaterial, in developing electronic devices such as liquid crystaldisplay, organic electroluminescence (EL) element (organic EL displayand organic EL lighting), touch panel, optical semiconductor (LED)element, solid-state image sensor, organic thin-film solar cell,dye-sensitized solar cell, and organic thin-film transistor (TFT).

Specific properties required therefor include 1) heat resistance, 2)transparency, 3) high refractive index, 4) high solubility, 5) lowvolume shrinkage, 6) hot-humid resistance, and 7) high film hardness.

In this regard, the present applicant has already found that a polymerthat contains a repeating unit having a triazine ring and an aromaticring demonstrates a high refractive index; that such polymer canachieve, solely by itself, high heat resistance, high transparency, highrefractive index, high solubility, and low volume shrinkage; and thatthe polymer is therefore suitable for a film-forming composition whenmanufacturing the electronic devices (Patent Literature 1).

A planarization layer or a light scattering layer, for example, of theorganic EL lighting has been formed usually by coating, with use of acomposition prepared by dissolving a high refractive index material inan organic solvent, occasionally prohibiting use of a high polaritysolvent on some sort of transparent electroconductive film.

Another problem can arise when coating a film-forming composition thatcontains a high refractive index polymer with use of a coater,occasionally followed by line cleaning of the device with use alow-polarity solvent, the line would be clogged if the polymer is lesssoluble to such solvent. Furthermore, when exposing the film to thesolvent during manufacture of the electronic device, the formed filmwould get cracks under some condition, calling for further improvementin the durability.

CITATION LIST Patent Literature

Patent Literature 1: WO 2010/128661

SUMMARY OF INVENTION Technical Problem

The present invention has been conceived in consideration of theaforementioned circumstances, and an object of which is to provide atriazine ring-containing polymer capable of forming a film that has highrefractive index and excels in transparency and solvent resistance(crack resistance), and is highly soluble in various organic solventssuch as low-polarity solvent, hydrophobic solvent, and low-boiling pointsolvent; and a film-forming composition containing the same.

Solution to Problem

After thorough investigations aimed at achieving the object, the presentinventors have found that a triazine ring-containing polymer capable offorming a film that has high refractive index and excels in transparencyand solvent resistance, and is highly soluble in various organicsolvents, is obtainable by using a triazine ring-containing polymerwhich has at least one triazine ring terminal, and at least a part ofthe triazine ring terminal is blocked with an arylamino group havingcrosslinking group.

That is, the present invention provides a triazine ring-containingpolymer, and a film-forming composition containing the same, as below.

[1] A triazine ring-containing polymer including a repeating unitstructure represented by formula (1) below, having at least one triazinering terminal, and at least a part of the triazine ring terminal beingblocked with an arylamino group having crosslinking group,

wherein each of R and R′ independently represents a hydrogen atom, analkyl group, an alkoxy group, an aryl group, or an aralkyl group, and

Ar represents at least one selected from the group represented byformulae (2) to (13),

wherein each of R¹ to R⁹² independently represents a hydrogen atom, ahalogen atom, a carboxy group, a sulfo group, an alkyl group having 1 to10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms,or an alkoxy group having 1 to 10 carbon atoms,

each of R⁹³ and R⁹⁴ represents a hydrogen atom or an alkyl group having1 to 10 carbon atoms,

each of W¹ and W² independently represents a single bond, CR⁹⁵R⁹⁶ (eachof R⁹⁵ and R⁹⁶ independently represents a hydrogen atom or an alkylgroup having 1 to 10 carbon atoms (where, they may form a ringtogether)), C═O, O, S, SO, SO₂, or NR⁹⁷ (R⁹⁷ represents a hydrogen atom,an alkyl group having 1 to 10 carbon atoms, or a phenyl group),

each of X¹ and X² independently represents a single bond, an alkylenegroup having 1 to 10 carbon atoms, or a group represented by formula(14),

wherein each of R⁹⁸ to R¹⁰¹ independently represents a hydrogen atom, ahalogen atom, a carboxy group, a sulfo group, an alkyl group having 1 to10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms,or an alkoxy group having 1 to 10 carbon atoms, and

each of Y¹ and Y² independently represents a single bond or an alkylenegroup having 1 to 10 carbon atoms.

[2] The triazine ring-containing polymer according to [1], wherein eachof R¹ to R⁹² and R⁹⁸ to R¹⁰¹ independently represents a hydrogen atom, ahalogen atom, or a halogenated alkyl group having 1 to 10 carbon atoms.[3] The triazine ring-containing polymer according to [1] or [2],wherein the arylamino group having crosslinking group is represented byformula (15),

wherein R¹⁰² represents a crosslinking group.

[4] The triazine ring-containing polymer according to [3], wherein thearylamino group having crosslinking group is represented by formula(16),

wherein R¹⁰² is synonymous as above.

[5] The triazine ring-containing polymer according to any one of [1] to[4], wherein the crosslinking group is a hydroxy-containing group or a(meth)acryloyl-containing group.[6] The triazine ring-containing polymer according to [5], wherein thecrosslinking group is a hydroxyalkyl group, a (meth)acryloyloxyalkylgroup, or a group represented by formula (i) below,

wherein A¹ represents an alkylene group having 1 to 10 carbon atoms, andA² represents a single bond or a group represented by formula (j) below,

wherein A³ represents a divalent or trivalent aliphatic hydrocarbongroup optionally substituted with hydroxy group, A⁴ represents ahydrogen atom or a methyl group, a represents 1 or 2, and * represents asite of bonding.

[7] The triazine ring-containing polymer according to [6], wherein thecrosslinking group is one or more groups selected from hydroxymethylgroup, 2-hydroxyethyl group, (meth)acryloyloxymethyl group,(meth)acryloyloxyethyl group, and groups represented by formulae (i-2)to (i-5) below,

wherein * represents a site of bonding.

[8] The triazine ring-containing polymer according to any one of [1] to[7], wherein at least one aromatic ring in Ar contains at least onehalogen atom or a halogenated alkyl group having 1 to 10 carbon atoms.[9] The triazine ring-containing polymer according to any one of [1] to[8], wherein a part of the triazine ring terminal is further blockedwith a non-substituted arylamino group.[10] The triazine ring-containing polymer according to any one of [1] to[9], wherein the non-substituted arylamino group is represented byformula (33).

[11] The triazine ring-containing polymer according to any one of [1] to[10], wherein Ar is represented by formula (17).

[12] The triazine ring-containing polymer according to any one of [1] to[10], wherein Ar is represented by formula (20).

[13] A film-forming composition that contains the triazinering-containing polymer according to any one of [1] to [12], and anorganic solvent.[14] The film-forming composition according to [13], wherein the organicsolvent is at least one selected from glycol ester-based solvent,ketone-based solvent, and ester-based solvent.[15] The film-forming composition according to [13] or [14], furthercontaining a crosslinking agent.[16] The film-forming composition according to [15], wherein thecrosslinking agent is a polyfunctional (meth)acrylic compound.[17] A film obtained from the film-forming composition according to anyone of [13] to [16].[18] An electronic device that contains a base, and the film accordingto [17] formed on the base.[19] An optical component that contains a base, and the film accordingto [17] formed on the base.

Advantageous Effects of Invention

The present invention can provide a triazine ring-containing polymercapable of forming a film that has high refractive index and excels intransparency and solvent resistance, and is highly soluble in variousorganic solvents such as low-polarity solvent, hydrophobic solvent, andlow-boiling point solvent.

With use of the triazine ring-containing polymer of the presentinvention, it now becomes possible to prepare the composition by usingan organic solvent with low solubilizing power, such as low-polaritysolvent or hydrophobic solvent, enabling formation of a film withoutproblem even on a base susceptible to erosion with high polaritysolvent.

Since the thin film formed of the composition for film formation of thepresent invention can demonstrate characteristics including high heatresistance, high refractive index, low volume shrinkage, and solventresistance (crack resistance), the thin film is therefore suitablyapplicable to the fields of electronic devices and optical materials,when manufacturing a part of liquid crystal display, an organic ELelement (organic EL display or organic EL lighting), touch panel,optical semiconductor (LED) element, solid-state image sensor, organicthin-film solar cell, dye-sensitized solar cell, organic thin-filmtransistor (TFT), lens, prism, camera, binoculars, microscope,semiconductor exposure apparatus, and the like.

In particular, the film formed of the film-forming composition of thepresent invention demonstrates high transparency and excels inrefractive index and solvent resistance (crack resistance), and cantherefore improve, when applied to a planarization layer or a lightscattering layer of organic EL lighting, the light extraction efficiency(light diffusion efficiency) and the durability thereof.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a ¹H-NMR spectral chart of compound P-1 (polymer compound [4])obtained in Example 1-1.

FIG. 2 is a ¹H-NMR spectral chart of compound P-2 (polymer compound [5])obtained in Example 1-2.

FIG. 3 is a ¹H-NMR spectral chart of compound P-3 (polymer compound [7])obtained in Example 1-3.

FIG. 4 is a ¹H-NMR spectral chart of compound P-4 (polymer compound [8])obtained in Comparative Example 1-1.

FIG. 5 is a ¹H-NMR spectral chart of compound P-5 (polymer compound [9])obtained in Comparative Example 1-2.

FIG. 6 is a ¹H-NMR spectral chart of compound P-6 (polymer compound[10]) obtained in Example 1-4.

FIG. 7 is an optical microphotograph of a surface of a cured filmobtained in Example 2-1, observed after exposed to a solvent.

FIG. 8 is an optical microphotograph of a surface of a cured filmobtained in Example 2-2, observed after exposed to a solvent.

FIG. 9 is an optical microphotograph of a surface of a cured filmobtained in Example 2-3, observed after exposed to a solvent.

FIG. 10 is an optical microphotograph of a surface of a cured filmobtained in Comparative Example 2-1, observed after exposed to asolvent.

FIG. 11 is an optical microphotograph of a surface of a cured filmobtained in Comparative Example 2-2, observed after exposed to asolvent.

FIG. 12 is a ¹H-NMR spectral chart of compound P-11 (polymer compound[15]) obtained in Example 3-1.

FIG. 13 is a ¹H-NMR spectral chart of compound P-12 (polymer compound[16]) obtained in Example 3-2.

FIG. 14 is a ¹H-NMR spectral chart of compound P-13 (polymer compound[19]) obtained in Comparative Example 3-1.

FIG. 15 is an optical microphotograph of a surface of a cured filmobtained in Example 3-1, observed.

FIG. 16 is an optical microphotograph of a surface of a cured filmobtained in Comparative Example 3-1, observed.

FIG. 17 is a ¹H-NMR spectral chart of compound P-22 (polymer compound[104]) obtained in Example 5-2.

FIG. 18 is an optical microphotograph of a surface of a cured filmobtained in Example 6-1, observed after exposed to a solvent.

FIG. 19 is an optical microphotograph of a surface of a cured filmobtained in Example 6-2, observed after exposed to a solvent.

DESCRIPTION OF EMBODIMENTS

The present invention will further be detailed.

The triazine ring-containing polymer of the present invention contains arepeating unit structure represented by formula (1) below.

The triazine ring-containing polymer is typically a so-calledhyperbranched polymer. The hyperbranched polymer is a highly branchedpolymer having an irregular branched structure. The term “irregular” asused herein means that it is more irregular than the branched structureof a dendrimer which is a highly branched polymer having a regularbranched structure.

For example, the triazine ring-containing polymer, being a hyperbranchedpolymer, includes a structure (structure A) having the repeating unitstructure represented by formula (1) bound to each of three bonds of therepeating unit structure represented by the formula (1), which iscontained as a structure larger than the repeating unit structurerepresented by formula (1). In the triazine ring-containing polymer,being a hyperbranched polymer, the structure A is distributedthroughout, but excluding the terminal of, the triazine ring-containingpolymer.

For example, the triazine ring-containing polymer, which is ahyperbranched polymer, includes a structure (structure A) formed bybound each of three sites of bonding of the repeating unit structurerepresented by formula (1) to the repeating unit structure representedby formula (1), and here the structure A is a structure larger than therepeating unit structure represented by formula (1). In the triazinering-containing polymer, being a hyperbranched polymer, the structure Ais distributed throughout, but excluding the terminal of, the triazinering-containing polymer.

In the triazine ring-containing polymer, being a hyperbranched polymer,the repeating unit structure may be substantially composed only of therepeating unit structure represented by formula (1).

In the formula, each of R and R independently represents a hydrogenatom, an alkyl group, an alkoxy group, an aryl group, or an aralkylgroup, wherein both of them preferably represent hydrogen atom from theviewpoint of further increasing the refractive index.

In the present invention, the number of carbon atoms of the alkyl groupis preferably, but not specifically limited to, 1 to 20. Inconsideration of further enhancing the heat resistance of the polymer,the number of carbon atoms of the alkyl group is more preferably 1 to10, and even more preferably 1 to 3. The structure of the alkyl group isnot particularly limited, and may typically be chain-like, branched,cyclic, or combinations of two or more of them.

The alkyl group is specifically exemplified by methyl, ethyl, n-propyl,isopropyl, cyclopropyl, n-butyl, isobutyl, s-butyl, t-butyl, cyclobutyl,1-methyl-cyclopropyl, 2-methyl-cyclopropyl, n-pentyl, 1-methyl-n-butyl,2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl,1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl,cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl,3-methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3-dimethyl-cyclopropyl,1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, n-hexyl, 1-methyl-n-pentyl,2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl,1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl,2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl,1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl,1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl,1-ethyl-2-methyl-n-propyl, cyclohexyl, 1-methyl-cyclopentyl,2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl,2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl,1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl,2,3-dimethyl-cyclobutyl, 2,4-dimethyl-cyclobutyl,3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl,1-isopropyl-cyclopropyl, 2-isopropyl-cyclopropyl,1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl,2,2,3-trimethyl-cyclopropyl, 1-ethyl-2 methyl-cyclopropyl,2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, and2-ethyl-3-methyl-cyclopropyl groups.

The number of carbon atoms of the alkoxy group is preferably, but notspecifically limited to, 1 to 20. In consideration of further enhancingthe heat resistance of the polymer, the number of carbon atoms of thealkoxy group is more preferably 1 to 10, and even more preferably 1 to3. The structure of the alkyl moiety is not particularly limited, andmay typically be chain-like, branched, cyclic, or combinations of two ormore of them.

The alkoxy group is specifically exemplified by methoxy, ethoxy,n-propoxy, isopropoxy, n-butoxy, isobutoxy, s-butoxy, t-butoxy,n-pentoxy, 1-methyl-n-butoxy, 2-methyl-n-butoxy, 3-methyl-n-butoxy,1,1-dimethyl-n-propoxy, 1,2-dimethyl-n-propoxy, 2,2-dimethyl-n-propoxy,1-ethyl-n-propoxy, n-hexyloxy, 1-methyl-n-pentyloxy,2-methyl-n-pentyloxy, 3-methyl-n-pentyloxy, 4-methyl-n-pentyloxy,1,1-dimethyl-n-butoxy, 1,2-dimethyl-n-butoxy, 1,3-dimethyl-n-butoxy,2,2-dimethyl-n-butoxy, 2,3-dimethyl-n-butoxy, 3,3-dimethyl-n-butoxy,1-ethyl-n-butoxy, 2-ethyl-n-butoxy, 1,1,2-trimethyl-n-propoxy,1,2,2-trimethyl-n-propoxy, 1-ethyl-1-methyl-n-propoxy, and1-ethyl-2-methyl-n-propoxy groups.

The number of carbon atoms of the aryl group is preferably, but notspecifically limited to, 6 to 40. In consideration of further enhancingthe heat resistance of the polymer, the number of carbon atoms of thearyl group is more preferably 6 to 16, and even more preferably 6 to 13.

In the present invention, the aryl group includes aryl group having asubstituent. The substituent is exemplified by halogen atom, alkyl grouphaving 1 to 6 carbon atoms, alkoxy group having 1 to 6 carbon atoms,nitro group, and cyano group.

The aryl group is specifically exemplified by phenyl, o-chlorophenyl,m-chlorophenyl, p-chlorophenyl, o-fluorophenyl, p-fluorophenyl,o-methoxyphenyl, p-methoxyphenyl, p-nitrophenyl, p-cyanophenyl,a-naphthyl, B-naphthyl, o-biphenylyl, m-biphenylyl, p-biphenylyl,1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl,3-phenanthryl, 4-phenanthryl, and 9-phenanthryl groups.

The number of carbon atoms of the aralkyl group is preferably, but notspecifically limited to, 7 to 20. The structure of the alkyl moiety isnot particularly limited, and may typically be straight chain-like,branched, cyclic, or combinations of two or more thereof.

In the present invention, the aralkyl group includes aralkyl grouphaving a substituent. The substituent is exemplified by halogen atom,alkyl group having 1 to 6 carbon atoms, alkoxy group having 1 to 6carbon atoms, nitro group, and cyano group.

Specific examples thereof include benzyl, p-methylphenylmethyl,m-methylphenylmethyl, o-ethylphenylmethyl, m-ethylphenylmethyl,p-ethylphenylmethyl, 2-propylphenylmethyl, 4-isopropylphenylmethyl,4-isobutylphenylmethyl, and an a-naphthylmethyl groups.

The Ar represents at least one group selected from those represented byformulae (2) to (13).

Each of R¹ to R⁹² independently represents a hydrogen atom, a halogenatom, a carboxy group, a sulfo group, an alkyl group having 1 to 10carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, oran alkoxy group having 1 to 10 carbon atoms, each of R⁹³ and R⁹⁴represents a hydrogen atom or an alkyl group having 1 to 10 carbonatoms, and each of W¹ and W² independently represents a single bond,CR⁹⁵R⁹⁶ (each of R⁹⁵ and R⁹⁶ independently represent a hydrogen atom oran alkyl group having 1 to 10 carbon atoms (where, they may form a ringtogether)), C═O, O, S, SO, SO₂, or NR⁹⁷ (R⁹⁷ represents a hydrogen atom,an alkyl group having 1 to 10 carbon atoms, or a phenyl group).

The halogen atom is exemplified by fluorine atom, chlorine atom, bromineatom, and iodine atom.

The alkyl group and the alkoxy group may be exemplified by those similarto the alkyl group and the alkoxy group represented by R and R′.

The halogenated alkyl group having 1 to 10 carbon atoms results fromsubstitution of at least one hydrogen atom in the alkyl group having 1to 10 carbon atoms with halogen atom, and is specifically exemplified bytrifluoromethyl, 2,2,2-trifluoroethyl, perfluoroethyl,3,3,3-trifluoropropyl, 2,2,3,3,3-pentafluoropropyl,2,2,3,3-tetrafluoropropyl, 2,2,2-trifluoro-1-(trifluoromethyl)ethyl,perfluoropropyl, 4,4,4-trifluorobutyl, 3,3,4,4,4-pentafluorobutyl,2,2,3,3,4,4,4-heptafluorobutyl, perfluorobutyl,2,2,3,3,4,4,5,5,5-nonafluoropentyl, 2,2,3,3,4,4,5,5-octafluoropentyl,perfluoropentyl, 2,2,3,3,4,4,5,5,6,6,6-undecafluorohexyl,2,2,3,3,4,4,5,5,6,6-decafluorohexyl, 3,3,4,4,5,5,6,6,6-nonafluorohexyl,and perfluorohexyl groups. Considering enhancement of the solubility ofthe triazine ring-containing polymer typically in low-polarity solventwhile maintaining the refractive index, particularly preferred in thisinvention is perfluoroalkyl group having 1 to 10 carbon atoms, morepreferred is perfluoroalkyl group having 1 to 5 carbon atoms, and evenmore preferred is trifluoromethyl group.

Each of X¹ and X² independently represents a single bond, an alkylenegroup having 1 to 10 carbon atoms, or a group represented by formula(14).

The structures of these alkyl group, halogenated alkyl group, alkoxygroup and alkylene group are not specifically limited, and may typicallybe chain-like, branched, cyclic, or combinations of two or more of them.

Each of R⁹⁸ to R¹⁰¹ independently represents a hydrogen atom, a halogenatom, a carboxy group, a sulfo group, an alkyl group having 1 to 10carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, oran alkoxy group having 1 to 10 carbon atoms, and each of Y¹ and Y²independently represents a single bond or an alkylene group having 1 to10 carbon atoms. These halogen atom, alkyl group, halogenated alkylgroup, and alkoxy group are exemplified by those similar to halogenatom, alkyl group, halogenated alkyl group, alkoxy group represented byR¹ to R⁹².

The alkylene group having 1 to 10 carbon atoms is exemplified bymethylene, ethylene, propylene, trimethylene, tetramethylene, andpentamethylene groups.

The structure of the alkyl group is not particularly limited, and maytypically be chain-like, branched, cyclic, or combinations of two ormore of them.

Among them, each of R¹ to R⁹² and R⁹⁸ to R¹⁰¹ preferably represents ahydrogen atom, a halogen atom, a sulfo group, an alkyl group having 1 to5 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, oran alkoxy group having 1 to 5 carbon atoms, wherein a hydrogen atom ismore preferred.

The triazine ring-containing polymer of the present invention preferablyhas at least one halogen atom or a halogenated alkyl group having 1 to10 carbon atoms, in at least one aromatic ring, from among the aromaticrings contained in Ar. Although introduction of fluorine atom into acompound has been known to often decrease the refractive index thereof,the triazine ring-containing polymer of the present invention maintainsa refractive index exceeding 1.7 despite the introduction of fluorineatom. Although the number of halogen atom or halogenated alkyl group inthe aromatic ring is freely selectable within a possibly largest numberof substitution on the aromatic ring, the number is preferably 1 to 4,more preferably 1 or 2, and even more preferably 1, in consideration ofthe balance between maintenance of the refractive index and solubilityin the solvent. Note in a case where the aromatic ring is a condensedring formed of a plurality of aromatic rings, like a naphthalene ring,such ring may only have at least one group as a whole.

Also note in a case where Ar contains a plurality of aromatic rings, itsuffices that at least one aromatic ring may contain at least onehalogen atom or a halogenated alkyl group, wherein each of all aromaticrings preferably contains at least one halogen atom or halogenated alkylgroup, and each of all aromatic rings more preferably contains onehalogen atom or halogenated alkyl group.

In particular, Ar preferably represents at least one group representedby formulae (2), and (5) to (13), and more preferably represents atleast one group represented by formulae (2), (5), (7), (8), and (11) to(13). The aryl group represented by formulae (2) to (13) arespecifically exemplified by, but not limited to, those represented bythe formulae below.

“Ph” represents a phenyl group.

wherein each A independently represents a halogen atom or a halogenatedalkyl group having 1 to 10 carbon atoms, each p independently representsan integer of 0 to 4, each q independently represents an integer of 0 to3, each r independently represents an integer of 0 to 2, each sindependently represents an integer of 0 to 5, t represents an integerof 1 to 6, and u represents an integer of 1 to 4, where, in each group,p, q, r and s totals 1 or higher. “Ph” represents a phenyl group.

Among them, more preferred is an aryl group represented by formulabelow, from the viewpoint of obtaining the polymer with higherrefractive index.

“Ph” represents a phenyl group.

wherein A, p, q, r, and u are synonymous as above. “Ph” represents aphenyl group.

In particular, in consideration of further enhancing the solubility ofthe triazine ring-containing polymer in an organic solvent such aslow-polarity solvent, Ar preferably represents m-phenylene grouprepresented by formula (17).

In particular, in consideration of further increasing the refractiveindex of the triazine ring-containing polymer, Ar preferably representsa group having a diphenyl ether skeleton represented by formulae (18) to(20).

wherein A and p are synonymous as above.

wherein A and p are synonymous as above.

The triazine ring-containing polymer of the present invention has atleast one triazine ring terminal, and at least a part of the triazinering terminal is blocked with an arylamino group having crosslinkinggroup.

The triazine ring-containing polymer of the present invention has atleast one triazine ring terminal, and such triazine ring at the terminalusually has two halogen atoms which can be substituted with thearylamino group having crosslinking group. Hence, the arylamino grouphaving crosslinking group may be bonded to the same triazine ringterminal, or may alternatively be bonded to different triazine ringterminals if there are a plurality of triazine ring terminals.

An aryl group in the arylamino group having crosslinking group isexemplified by groups same as those described above, for which phenylgroup is particularly preferred.

The crosslinking group is bonded to the aryl group.

The crosslinking group is exemplified by hydroxy-containing group,vinyl-containing group, epoxy-containing group, oxetane-containinggroup, carboxy-containing group, sulfo-containing group,thiol-containing group, and (meth)acryloyl-containing group, among whichhydroxy-containing group and (meth)acryloyl-containing group arepreferred, in consideration of improving heat resistance of the triazinering-containing polymer, and solvent resistance (crack resistance) ofthe obtainable film.

The hydroxy-containing group is exemplified by hydroxy group andhydroxyalkyl group, among which hydroxyalkyl group having 1 to 10 carbonatoms is preferred, hydroxyalkyl group having 1 to 5 carbon atoms ismore preferred, and hydroxyalkyl group having 1 to 3 carbon atoms iseven more preferred.

The hydroxyalkyl group having 1 to 10 carbon atoms is exemplified bythose having a hydroxy group bonded to a primary carbon atom, such ashydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl,5-hydroxypentyl, 6-hydroxyhexyl, 7-hydroxyheptyl, 8-hydroxyoctyl,9-hydroxynonyl, 10 hydroxydecyl, 2-hydroxy-1-methylethyl,2-hydroxy-1,1-dimethylethyl, 3-hydroxy-1-methylpropyl,3-hydroxy-2-methylpropyl, 3-hydroxy-1,1-dimethylpropyl,3-hydroxy-1,2-dimethylpropyl, 3-hydroxy-2,2-dimethylpropyl,4-hydroxy-1-methylbutyl, 4-hydroxy-2-methylbutyl, and4-hydroxy-3-methylbutyl groups; and those having a hydroxy group bondedto a secondary or tertiary carbon atoms, such as 1-hydroxyethyl,1-hydroxypropyl, 2-hydroxypropyl, 1-hydroxybutyl, 2-hydroxybutyl,1-hydroxyhexyl, 2-hydroxyhexyl, 1-hydroxyoctyl, 2-hydroxyoctyl,1-hydroxydecyl, 2-hydroxydecyl, 1-hydroxy-1-methylethyl, and 2-hydroxy-2methylpropyl groups.

In particular, in consideration of improving heat resistance andhot-humid resistance, preferred are those having a hydroxy group bondedto a primary carbon atom, among which preferred is hydroxyalkyl grouphaving 1 to 5 carbon atoms, more preferred is hydroxyalkyl group having1 to 3 carbon atoms, even more preferred are hydroxymethyl group and2-hydroxyethyl group, and most preferred is 2-hydroxyethyl group.

The (meth)acryloyl-containing group is exemplified by (meth)acryloylgroup, (meth)acryloyloxyalkyl group, and group represented by formula(i) below, among which preferred are (meth)acryloyloxyalkyl group havingan alkylene group having 1 to 10 carbon atoms, and the group representedby formula (i) below, and more preferred is the group represented byformula (i) below.

wherein A¹ represents an alkylene group having 1 to 10 carbon atoms, andA² represents a single bond or a group represented by formula (j) below,

wherein A³ represents a divalent or trivalent aliphatic hydrocarbongroup optionally substituted with hydroxy group, A⁴ represents ahydrogen atom or a methyl group, a represents 1 or 2, and * represents asite of bonding.

The alkylene group contained in the (meth)acryloyloxyalkyl group havingan alkylene group (alkanediyl group) having 1 to 10 carbon atoms isexemplified by methylene, ethylene, trimethylene, propane-1,2-diyl,tetramethylene, butane-1,3-diyl, butane-1,2-diyl,2-methylpropane-1,3-diyl, pentamethylene, hexamethylene, heptamethylene,octamethylene, nonamethylene, and decimethylene groups. Among them,those having an alkylene group having 1 to 5 carbon atoms are preferred,in consideration of improving heat resistance and hot-humid resistance,those having an alkylene group having 1 to 3 carbon atoms are morepreferred, and those having an alkylene group having 1 or 2 carbon atomsare even more preferred.

The (meth)acryloyloxyalkyl group is specifically exemplified by(meth)acryloyloxymethyl group, 2-(meth)acryloyloxyethyl group,3-(meth)acryloyloxypropyl group, and 4-(meth)acryloyloxybutyl group.

In formula (i), A¹ represents an alkylene group having 1 to 10 carbonatoms, preferably represents an alkylene group having 1 to 5 carbonatoms, and more preferably represents a methylene group or an ethylenegroup. The alkylene group having 1 to 10 carbon atoms is exemplified byalkylene groups same as those contained in the aforementioned(meth)acryloyloxyalkyl group.

A² Represents a single bond or a group represented by formula (j), amongwhich a group represented by formula (j) is preferred.

A³ represents a divalent or trivalent aliphatic hydrocarbon groupoptionally substituted with hydroxy group, and is specificallyexemplified by alkylene group having 1 to 5 carbon atoms, and a grouprepresented by formulae (k-1) to (k-3) below:

wherein * is synonymous as above.

Among which alkylene group having 1 to 5 carbon atoms is preferred,alkylene group having 1 to 3 carbon atoms is more preferred, andmethylene group and ethylene group are even more preferred. The alkylenegroup represented by A³ is exemplified by alkylene group having 1 to 5carbon atoms, from among the alkylene groups exemplified for A¹.

a Represents 1 or 2, wherein 1 is preferred.

Preferred embodiments of the group represented by formula (i) areexemplified by those represented by formula (i-1) below.

wherein A¹, A³, A⁴ and * are synonymous as above.

More preferred embodiments of the group represented by formula (i) areexemplified by those represented by formulae (i-2) to (i-5) below.

wherein * is synonymous as above.

The vinyl-containing group is exemplified by alkenyl group having 2 to10 carbon atoms, and having a vinyl group at the terminal. Specificexamples include ethenyl, 1-propenyl, allyl, isopropenyl, 1-butenyl,2-butenyl, and 2-pentenyl groups.

The epoxy-containing group is exemplified by epoxy, glycidyl, andglycidyloxy groups. Specific examples include glycidylmethyl,2-glycidylethyl, 3-glycidylpropyl, and 4-glycidylbutyl groups.

The oxetane-containing group is exemplified by oxetane-3-yl,(oxetane-3-yl)methyl, 2-(oxetane-3-yl)ethyl, 3-(oxetane-3-yl)propyl, and4-(oxetane-3-yl)butyl groups.

The carboxy-containing group is exemplified by carboxy group andcarboxyalkyl group having 2 to 10 carbon atoms. The carboxyalkyl grouphaving 2 to 10 carbon atoms is preferably any of those having a carboxygroup bonded to a primary carbon atom, and is specifically exemplifiedby carboxymethyl, 2-carboxyethyl, 3-carboxypropyl, and 4-carboxybutylgroups.

The sulfo-containing group is exemplified by sulfo group, and sulfoalkylgroup having 1 to 10 carbon atoms. The sulfoalkyl group having 1 to 10carbon atoms is preferably any of those having a sulfo group bonded to aprimary carbon atom, and is specifically exemplified by sulfomethyl,2-sulfoethyl, 3-sulfopropyl, and 4-sulfobutyl groups.

The thiol-containing group is exemplified by thiol group, andmercaptoalkyl group having 1 to 10 carbon atoms. The mercaptoalkyl grouphaving 1 to 10 carbon atoms is preferably any of those having a thiolgroup bonded to a primary carbon atom, and is specifically exemplifiedby mercaptomethyl, 2-mercaptoethyl, 3-mercaptopropyl, and4-mercaptobutyl groups.

Although the number of crosslinking group in the arylamino group havingcrosslinking group is freely selectable without special limitationwithin a possibly largest number of substitution on the aryl group, thenumber is preferably 1 to 4, in consideration of the balance betweensolvent resistance and solubility in solvent, which is more preferably 1or 2, and even more preferably 1.

Preferred arylamino group having crosslinking group is exemplified by agroup represented by formula (15), and is particularly preferablyexemplified by a group represented by formula (16), having acrosslinking group at the para-position relative to the amino group.

wherein R¹⁰² represents a crosslinking group.

wherein R¹⁰² is synonymous as above.

The arylamino group having crosslinking group is specificallyexemplified by, but not limited to, those represented by the formulaebelow.

The arylamino group having hydroxyalkyl group can be introduced by usinga corresponding hydroxyalkyl group-substituted arylamino compound, by amethod of production described later.

The hydroxyalkyl group-substituted arylamino compound is exemplified by(4-aminophenyl)methanol and 2-(4-aminophenyl)ethanol.

The arylamino group having (meth)acryloyloxyalkyl group can beintroduced by a method that uses a corresponding (meth)acryloyloxyalkylgroup-substituted arylamino compound; or by a method in which anarylamino group having hydroxyalkyl group is introduced into thetriazine ring-containing polymer, and then (meth)acrylic acid halide orglycidyl (meth)acrylate is further allowed to act on the hydroxy groupcontained in the hydroxyalkyl group.

The arylamino group having the group represented by formula (i) can beintroduced by a method that uses an arylamino compound having anintended crosslinking group; or by a method in which an arylamino grouphaving hydroxyalkyl group is introduced into the triazinering-containing polymer, and then (meth)acrylate ester compound havingisocyanate group, represented by formula (i′) below, is further allowedto act on the hydroxy group contained in the hydroxyalkyl group.

wherein A³, A⁴ and a are synonymous as above.

The (meth)acryloyloxyalkyl group-substituted arylamino compound isspecifically exemplified by ester compound obtainable by allowing(meth)acrylic acid halide or glycidyl (meth)acrylate to act on thehydroxy group of the hydroxyalkyl group-substituted arylamino compound.

The (meth)acrylic acid halide is exemplified by (meth)acryloyl chloride,(meth)acryloyl bromide, and (meth)acryloyl iodide.

The (meth)acrylate ester compound having isocyanate group, representedby formula (i′), is exemplified by 2-isocyanatoethyl acrylate,2-isocyanatoethyl methacrylate, and 1,1-(bisacryloyloxymethyl)ethylisocyanate. From the viewpoint of simplicity in synthesis method,2-isocyanatoethyl acrylate is preferred in the present invention.

In the present invention, particularly preferred triazinering-containing polymer is exemplified by those containing repeatingunits represented by formulae (21) to (28) below.

wherein R, R′, R¹ to R⁴ and R¹⁰² are synonymous as above.

wherein R¹ to R⁴ and R¹⁰² are synonymous as above.

wherein R¹⁰² is synonymous as above.

wherein R¹⁰² is synonymous as above.

wherein R, R¹, R¹⁶ to R²³ and R¹⁰² are synonymous as above.

wherein R¹⁶ to R²³ and R¹⁰² are synonymous as above.

wherein R¹⁰² is synonymous as above.

wherein R¹⁰² is synonymous as above.

Weight average molecular weight of the polymer in the present invention,although not particularly limited, is preferably 500 to 500,000, andmore preferably 500 to 100,000. From the viewpoint of further improvingthe heat resistance and decreasing the shrinkage rate, it is morepreferably 2,000 or higher, and from the viewpoint of further improvingthe solubility and of decreasing the viscosity of the obtainablesolution, it is preferably 50,000 or lower, more preferably 30,000 orlower, even more preferably 25,000 or lower, and most preferably 10,000or lower.

The weight average molecular weight in the present invention is anaverage molecular weight in terms of standard polystyrene, obtainable bygel permeation chromatography (referred to as GPC, hereinafter).

The triazine ring-containing polymer of the present invention(hyperbranched polymer) may be produced referring to the methoddisclosed in WO 2010/128661.

That is, the triazine ring-containing polymer of the present inventionis obtainable by reacting a trihalogenated triazine compound with anaryldiamino compound in an organic solvent, and then by further reactingfor example with, as a terminal blocking agent, at least one arylaminocompound selected from arylamino compound having hydroxyalkyl group(hydroxy-containing group), arylamino compound having acryloyloxyalkylgroup (acryloyl-containing group), and arylamino compound having grouprepresented by formula (i) (acryloyl-containing group).

For example, as illustrated in scheme 1 below, a triazinering-containing polymer (23) is obtainable by reacting a triazinecompound (29) with an aryldiamino compound (30) in an appropriateorganic solvent, and by further reacting with, as a terminal blockingagent, at least one arylamino compound (31) selected from the arylaminocompound having hydroxyalkyl group, and the arylamino compound havingthe group represented by formula (i).

wherein each X independently represents a halogen atom, and R^(a)represents a hydroxyalkyl group, or a group represented by formula (i).

Alternatively, typically as illustrated in scheme 2 below, a triazinering-containing polymer (27) is obtainable by reacting the triazinecompound (29) with an aryldiamino compound (32) in an appropriateorganic solvent, and by further reacting with, as a terminal blockingagent, at least one arylamino compound (31) selected from the arylaminocompound having hydroxyalkyl group, and the arylamino compound havingthe group represented by formula (i).

wherein each X independently represents a halogen atom, and R^(a)represents a hydroxyalkyl group, or a group represented by formula (i).

In scheme 1 or scheme 2 above, loading ratio of the aryldiamino compound(30) or (32) is freely selectable so long as an intended polymer isobtainable, wherein the aryldiamino compound (30) or (32) preferablyaccounts for 0.01 to 10 equivalents per one equivalent of the triazinecompound (29), and more preferably accounts for 0.7 to 5 equivalents.

The aryldiamino compound (30) or (32) may be added neat, or in the formof solution after dissolved in organic solvent, wherein the lattertechnique is preferred in consideration of simplicity of operation andeasiness of reaction control.

Reaction temperature may be suitably preset within the range from themelting point up to the boiling point of the solvent to be employed,which is preferably around −30 to 150° C., and more preferably around−10 to 100° C.

Another embodiment is exemplified by a technique illustrated in scheme 3below. In this technique, the triazine ring-containing polymer (23) isobtainable by reacting the triazine compound (29) with the aryldiaminocompound (30) in an appropriate organic solvent, and by further reactingwith, as a terminal blocking agent, an arylamino compound (31′) havinghydroxyalkyl group, to obtain a triazine ring-containing polymer (23′)(first stage); then by allowing a (meth)acrylate ester compound havingisocyanate group represented by formula (i′) to act on the hydroxy groupof the hydroxyalkyl group contained in the triazine ring-containingpolymer (23′) (second stage).

In a case where the triazine ring-containing polymer (23′) is desired asa final product, the scheme may be terminated upon completion of thefirst stage, without proceeding to the reaction in the second stage.

wherein R^(a1) represents a hydroxyalkyl group, and X, A³, A⁴, R^(a) anda are synonymous as above.

Still another embodiment is exemplified by a technique illustrated inscheme 4 below. In this technique, the triazine ring-containing polymer(27) is obtainable by reacting the triazine compound (29) with thearyldiamino compound (32) in an appropriate organic solvent, and byfurther reacting with, as a terminal blocking agent, an arylaminocompound (31′) having hydroxyalkyl group, to obtain a triazinering-containing polymer (27′) (first stage); then by allowing the(meth)acrylate ester compound having isocyanate group represented byformula (i′) to act on the hydroxy group of the hydroxyalkyl groupcontained in the triazine ring-containing polymer (27′) (second stage).

In a case where the triazine ring-containing polymer (27′) is desired asa final product, the scheme may be terminated upon completion of thefirst stage, without proceeding to the reaction in the second stage.

wherein R^(a1) represents a hydroxyalkyl group, and X, A³, A⁴, R^(a) anda are synonymous as above.

In scheme 3 above, the loading ratio and the way of addition of thearyldiamino compound (30) in the first stage, and the reactiontemperature throughout the reaction to obtain the triazinering-containing polymer (23′) may be similar to those described inscheme 1.

In the second stage, the loading ratio of the (meth)acrylate estercompound having isocyanate group represented by formula (i′), relativeto the triazine ring-containing polymer (23′), may be freely selectabledepending on the ratio of the hydroxyalkyl group to the grouprepresented by formula (i), which is preferably 0.1 to 10 equivalents,more preferably 0.5 to 5 equivalents, even more preferably 0.7 to 3equivalents, and yet more preferably 0.9 to 1.5 equivalents, per oneequivalent of the arylamino compound having hydroxyalkyl group to beemployed. Assuming now, for example, that all of the hydroxyalkyl groupscontained in the triazine ring-containing polymer (23′) were the groupsrepresented by formula (i), the loading ratio of the (meth)acrylateester compound, per one equivalent of the arylamino compound havinghydroxyalkyl group to be employed, is preferably 1.0 to 10 equivalents,more preferably 1.0 to 5 equivalents, even more preferably 1.0 to 3equivalents, and yet more preferably 1.0 to 1.5 equivalents.

Although the reaction temperature in the reaction may be equivalent tothe reaction temperature in the reaction for obtaining the triazinering-containing polymer (23′), the temperature is preferably 30 to 80°C. in consideration of preventing the (meth)acryloyl group frompolymerizing during the reaction, more preferably 40 to 70° C., and evenmore preferably 50 to 60° C.

In scheme 4 above, the loading ratio and the way of addition of thearyldiamino compound (32) in the first stage, and the reactiontemperature throughout the reaction to obtain the triazinering-containing polymer (27′) may be similar to those described inscheme 2.

In the second stage, the loading ratio of the (meth)acrylate estercompound having isocyanate group represented by formula (i′), relativeto the triazine ring-containing polymer (27′), may be freely selectabledepending on the ratio of the hydroxyalkyl group to the grouprepresented by formula (i), which is preferably 0.1 to 10 equivalents,more preferably 0.1 to 5 equivalents, even more preferably 0.1 to 3equivalents, and yet more preferably 0.1 to 1.05 equivalents, per oneequivalent of the arylamino compound having hydroxyalkyl group to beemployed. Assuming now, for example, that all of the hydroxyalkyl groupscontained in the triazine ring-containing polymer (22′) were the groupsrepresented by formula (i), the loading ratio of the (meth)acrylateester compound, per one equivalent of the arylamino compound havinghydroxyalkyl group to be employed, is preferably 1.0 to 10 equivalents,more preferably 1.0 to 5 equivalents, even more preferably 1.0 to 3equivalents, and yet more preferably 1.0 to 1.05 equivalents.

Although the reaction temperature in the reaction may be equivalent tothe reaction temperature in the reaction for obtaining the triazinering-containing polymer (27′), the temperature is preferably 30 to 80°C. in consideration of preventing the (meth)acryloyl group frompolymerizing during the reaction, more preferably 40 to 70° C., and evenmore preferably 50 to 60° C.

In the second stages of scheme 3 and scheme 4, the reaction may beconducted in the presence of a polymerization inhibitor so that the(meth)acryloyl group would not polymerize during the reaction.

The polymerization inhibitor is exemplified byN-methyl-N-nitrosoaniline, N-nitrosophenylhydroxylamine or saltsthereof, benzoquinones, phenol-based polymerization inhibitor, andphenothiazine. Among them, N-nitrosophenylhydroxylamine or salts thereofare preferred from the viewpoint of excellent effect of polymerizationinhibition.

The salts of N-nitrosophenylhydroxylamine are exemplified byN-nitrosophenylhydroxyamine ammonium salt andN-nitrosophenylhydroxyamine aluminum salt.

The benzoquinones are exemplified by p-benzoquinone and2-methyl-1,4-benzoquinone.

The phenol-based polymerization inhibitor is exemplified byhydroquinone, p-methoxyphenol, 4-t-butylcatechol, 2-t-butylhydroquinone,and 2,6-di-t-butyl-4-methylphenol.

The amount of consumption of the polymerization inhibitor may typicallybe, but not specially limited to, 1 to 200 ppm in mass ratio relative tothe (meth)acrylate ester compound having isocyanate group represented byformula (i′), or may be 10 to 100 ppm.

By using the polymerization inhibitor, the reaction in the second stagemay be conducted while suppressing the polymerization of the(meth)acryloyl group, even at the reaction temperature elevated up toaround 60 to 80° C.

The organic solvent may be any of various solvents usually employed forthis sort of reaction, and is exemplified by tetrahydrofuran (THF);dioxane; dimethyl sulfoxide; and amide-based solvents such asN,N-dimethylformamide, N-methyl-2-pyrrolidone, tetramethylurea,hexamethylphosphoramide, N,N-dimethylacetamide, N-methyl-2-piperidone,N,N-dimethylethyleneurea, N,N,N′,N′-tetramethylmalonic acid amide,N-methylcaprolactam, N-acetylpyrrolidine, N,N-diethylacetamide,N-ethyl-2-pyrrolidone, N,N-dimethylpropionic acid amide,N,N-dimethylisobutyramide, N-methylformamide, andN,N′-dimethylpropyleneurea; and mixed solvents of them.

Among them, preferred are N,N-dimethylformamide, dimethyl sulfoxide,N-methyl-2-pyrrolidone, N,N-dimethylacetamide, and mixed system thereof,and particularly preferred are N,N-dimethylacetamide andN-methyl-2-pyrrolidone.

In the reaction in the first stage of scheme 1 or scheme 2, any ofvarious bases which are usually used during or after polymerization maybe added.

The base is specifically exemplified by potassium carbonate, potassiumhydroxide, sodium carbonate, sodium hydroxide, sodium bicarbonate,sodium ethoxide, sodium acetate, lithium carbonate, lithium hydroxide,lithium oxide, potassium acetate, magnesium oxide, calcium oxide, bariumhydroxide, trilithium phosphate, trisodium phosphate, tripotassiumphosphate, cesium fluoride, aluminum oxide, ammonia, n-propylamine,trimethylamine, triethylamine, diisopropylamine, diisopropylethylamine,N-methylpiperidine, 2,2,6,6-tetramethyl-N-methylpiperidine, pyridine,4-dimethylaminopyridine, and N-methylmorpholine.

The amount of addition of the base is preferably 1 to 100 equivalentsper one equivalent of the triazine compound (29), and is more preferably1 to 10 equivalents. These bases may be used in the form of aqueoussolution.

Although the obtainable polymer is preferably free of residual rawmaterial, the raw material may partially remain without undermining theeffect of the present invention.

After completion of the reaction, the product may be easily purifiedtypically by reprecipitation.

Employable method of blocking the terminal with use of the arylaminocompound having crosslinking group may be any of known methods.

The amount of consumption of the terminal blocking agent in this case ispreferably about 0.05 to 10 equivalents, per one equivalent of halogenatom derived from excessive triazine compound remained unconsumed forthe polymerization reaction, which is more preferably 0.1 to 5equivalents, and even more preferably 0.5 to 2 equivalents.

The reaction solvent and the reaction temperature are exemplified by theconditions having been described regarding the reaction in theaforementioned first stage of scheme 1 or scheme 2 above. The terminalblocking agent may be loaded together with the aryldiamino compound (30)or (32).

Alternatively, the terminal may be blocked with two or more kinds ofgroups, with use of non-substituted arylamino compound having nocrosslinking group. An aryl group in the non-substituted arylaminocompound is exemplified by the groups same as those described above.

The non-substituted arylamino group is specifically exemplified by, butnot limited to, those represented by formula (33) below.

The non-substituted arylamino group may be introduced with use of acorresponding non-substituted aryl amino compound, by a method ofproduction described later.

The non-substituted arylamino compound is exemplified by aniline.

When introducing the non-substituted arylamino group, the ratio of thearylamino compound having crosslinking group and the non-substitutedarylamino compound is preferably 0.1 to 1.0 mol per 1 mol of thearylamino compound having crosslinking group, from the viewpoint ofdemonstrating solubility in the organic solvent and yellowing resistancein a well-balanced manner, wherein the ratio is more preferably 0.1 to0.5 mol, and even more preferably 0.1 to 0.3 mol.

The aforementioned triazine ring-containing polymer of the presentinvention is suitably applicable as a film-forming composition. In thiscase, a crosslinking agent may be added.

The crosslinking agent is not specifically limited so long as it is acompound having a substituent capable of reacting with the crosslinkinggroup of the aforementioned triazine ring-containing polymer.

This sort of compound is exemplified by melamine-based compound havingcrosslinkage-forming substituent such as methylol group or methoxymethylgroup (for example, phenoplast compound, aminoplast compound, etc.);substituted urea-based compound; compound having crosslinkage-formingsubstituent such as epoxy group or oxetane group (for example,polyfunctional epoxy compound, polyfunctional oxetane compound, etc.);compound having blocked isocyanate group; compound having acid anhydridegroup; and compound having (meth)acrylic group. From the viewpoint ofheat resistance and shelf stability, preferred are compound having epoxygroup, blocked isocyanate group, or (meth)acrylic group; andparticularly preferred are compound having blocked isocyanate group, andpolyfunctional epoxy compound and/or polyfunctional (meth)acryliccompound capable of yielding photocurable composition without usinginitiator.

Note that these compounds, when intended for termination of the polymer,may only have at least one crosslinkage-forming substituent, meanwhilethese compounds, when intended for crosslinking the polymers,necessarily have at least two crosslinkage-forming substituents.

The polyfunctional epoxy compound is not specifically limited so long asit has two or more epoxy groups per molecule.

Specific examples thereof include tris(2,3-epoxypropyl) isocyanurate,1,4-butanediol diglycidyl ether, 1,2-epoxy-4-(epoxyethyl)cyclohexane,glycerol triglycidyl ether, diethylene glycol diglycidyl ether,2,6-diglycidylphenyl glycidyl ether,1,1,3-tris[p-(2,3-epoxypropoxy)phenyl] propane,1,2-cyclohexanedicarboxylic acid diglycidyl ester,4,4′-methylenebis(N,N-diglycidylaniline),3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate,trimethylolethane triglycidyl ether, bisphenol-A-diglycidyl ether, andpentaerythritol polyglycidyl ether.

Commercially available products employable here include epoxy resinhaving at least two epoxy groups such as YH-434 and YH-434L (from NIPPONSTEEL Chemical & Materials Co., Ltd.);

epoxy resin having a cyclohexene oxide structure such as EPOLEAD GT-401,GT-403, GT-301 and GT-302, CELLOXIDE 2021 and 3000 (from DaicelCorporation); bisphenol A type epoxy resin such as jER 1001, 1002, 1003,1004, 1007, 1009, 1010 and 828 (all from Mitsubishi ChemicalCorporation); bisphenol F type epoxy resin such as jER807 (fromMitsubishi Chemical Corporation); phenol novolac type epoxy resin suchas jER 152 and 154 (both from Mitsubishi Chemical Corporation), EPPN201and 202 (both from Nippon Kayaku Co., Ltd.); cresol novolac type epoxyresin such as EOCN-102, 103S, 104S, 1020, 1025 and 1027 (all from NipponKayaku Co., Ltd.), jER180S75 (from Mitsubishi Chemical Corporation);alicyclic epoxy resin such as Denacol EX-252 (from Nagase ChemteXCorporation), CY-175, CY177, and CY179 (all from CIBA-GEIGY A.G.),Araldite CY-182, CY-192, and CY-184 (all from CIBA-GEIGY A.G.), EPICLON200 and 400 (both from DIC Corporation), jER 871 and 872 (both fromMitsubishi Chemical Corporation), ED-5661 and ED-5662 (both fromCeranise Coating Co., Ltd.); and aliphatic polyglycidyl ether such asDenacol EX-611, EX-612, EX-614, EX-622, EX-411, EX-512, EX-522, EX-421,EX-313, EX-314 and EX-321 (all from Nagase ChemteX Corporation).

The polyfunctional (meth)acryl compound is not specifically limited solong as it has two or more (meth)acryl groups per molecule.

Specific examples thereof include ethylene glycol diacrylate, ethyleneglycol dimethacrylate, polyethylene glycol diacrylate, polyethyleneglycol dimethacrylate, ethoxylated bisphenol A diacrylate, ethoxylatedbisphenol A dimethacrylate, ethoxylated trimethylolpropane triacrylate,ethoxylated trimethylolpropane trimethacrylate, ethoxylated glycerintriacrylate, ethoxylated glycerin trimethacrylate, ethoxylatedpentaerythritol tetraacrylate, ethoxylated pentaerythritoltetramethacrylate, ethoxylated dipentaerythritol hexaacrylate,polyglycerin monoethylene oxide polyacrylate, polyglycerin polyethyleneglycol polyacrylate, dipentaerythritol hexaacrylate, dipentaerythritolhexamethacrylate, neopentyl glycol diacrylate, neopentyl glycoldimethacrylate, pentaerythritol triacrylate, pentaerythritoltrimethacrylate, trimethylolpropane triacrylate, trimethylolpropanetrimethacrylate, tricyclodecane dimethanol diacrylate, tricyclodecanedimethanol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanedioldimethacrylate, dipropylene glycol diacrylate, tripropylene glycoldiacrylate, and polybasic acid-modified acrylic oligomer.

The polyfunctional (meth)acrylic compound is commercially available, andspecific examples thereof include NK Ester A-200, A-400, A-600, A-1000,and A-9300 (tris(2-acryloyloxyethyl) isocyanurate), A-9300-1CL, A-TMPT,UA-53H, 1G, 2G, 3G, 4G, 9G, 14G, 23G, ABE-300, A-BPE-4, A-BPE-6,A-BPE-10, A-BPE-20, A-BPE-30, BPE-80N, BPE-100N, BPE-200, BPE-500,BPE-900, BPE-1300N, A-GLY-3E, A-GLY-9E, A-GLY-20E, A-TMPT-3EO,A-TMPT-9EO, AT-20E, ATM-4E, ATM-35E, APG-100, and APG-200 (all fromShin-Nakamura Chemical Co., Ltd.), KAYARAD (registered trademark)DPEA-12, PEG400DA, THE-330, and RP-1040 (all from Nippon Kayaku Co.,Ltd.), ARONIX M-210 and M-350 (both from Toagosei Co., Ltd.), KAYARAD(registered trademark) DPHA, NPGDA, and PET30 (all from Nippon KayakuCo., Ltd.), NK Ester A-DPH, A-TMPT, A-DCP, A-HD-N, TMPT, DCP, NPG, andHD-N (all from Shin-Nakamura Chemical Co., Ltd.), NK Oligo U-15HA (fromShin-Nakamura Chemical Co., Ltd.), NK Polymer Vanaresin GH-1203 (fromShin-Nakamura Chemical Co., Ltd.), and DN-0075 (from Nippon Kayaku Co.,Ltd.).

Also the polybasic acid-modified acrylic oligomer is commerciallyavailable, and specific examples thereof include ARONIX M-510 and 520(both from Toagosei Co., Ltd.).

The compound having acid anhydride group is not specifically limited solong as it is a carboxylic acid anhydride obtained by dehydrationcondensation of two carboxylic acid molecules, and specific examplesthereof include compound having one acid anhydride group in themolecule, such as phthalic anhydride, tetrahydrophthalic anhydride,hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride,methylhexahydrophthalic anhydride, nadic anhydride, methylnadicanhydride, maleic anhydride, succinic anhydride, octylsuccinicanhydride, and dodecenylsuccinic anhydride; and compound having two acidanhydride groups in the molecule, such as1,2,3,4-cyclobutanetetracarboxylic dianhydride, pyromellitic anhydride,3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic dianhydride,bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic dianhydride,5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylicanhydride, 1,2,3,4-butanetetracarboxylic dianhydride,3,3′,4,4′-benzophenonetetracarboxylic dianhydride,3,3′,4,4′-biphenyltetracarboxylic dianhydride,2,2-bis(3,4-dicarboxyphenyl) hexafluoropropane dianhydride, and1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride.

The compound having blocked isocyanate group is not particularly limitedso long as it has, per molecule, two or more blocked isocyanate groupshaving an appropriate protecting group for blocking the isocyanate group(—NCO), and so long as it releases the protecting group (block moiety)as a result of thermal dissociation when exposed to high temperaturesduring heat curing, allowing the generated isocyanate group to causecrosslinking reaction with the crosslinking group (hydroxy-containinggroup, for example) of the triazine ring-containing polymer of thepresent invention. The compound is exemplified by those having, permolecule, two or more groups represented by the formula below (thesegroups may be the same or different) in one molecule.

wherein R^(b) represents an organic group in the blocking moiety.

This sort of compound is obtainable typically by reacting a compoundhaving, per molecule, two or more isocyanate groups with an appropriateblocking agent.

The compound having, per molecule, two or more isocyanate groups isexemplified by polyisocyanate such as isophorone diisocyanate,1,6-hexamethylene diisocyanate, methylenebis(4-cyclohexyl isocyanate),and trimethylhexamethylene diisocyanate; dimers and trimers thereof; andreaction products thereof with diols, triols, diamines, or triamines.

The blocking agent is exemplified by alcohols such as methanol, ethanol,isopropanol, n-butanol, 2-ethoxyhexanol, 2-N,N-dimethylaminoethanol,2-ethoxyethanol, and cyclohexanol; phenols such as phenol,o-nitrophenol, p-chlorophenol, and o-, m- or p-cresol; lactams such ass-caprolactam; oximes such as acetone oxime, methyl ethyl ketone oxime,methyl isobutyl ketone oxime, cyclohexanone oxime, acetophenone oxime,and benzophenone oxime; pyrazoles such as pyrazole,3,5-dimethylpyrazole, and 3-methylpyrazole; and thiols such asdodecanethiol and benzenethiol.

The compound having blocked isocyanate group is also commerciallyavailable, and is specifically exemplified by TAKENATE (registeredtrademark) B-830, B-815N, B-842N, B-870N, B-874N, B-882N, B-7005,B-7030, B-7075, and B-5010 (all from Mitsui Chemicals, Inc.), Duranate(registered trademark) 17B-60PX, TPA-B80E, MF-B60X, MF-K60X, andE402-B80T (all from Asahi Kasei Corporation), Karenz MOI-BM (registeredtrademark) (from Showa Denko K.K.), and Trixene (registered trademark)BI-7950, BI-7951, BI-7960, BI-7961, BI-7963, BI-7982, BI-7991, andBI-7992 (from Baxenden Chemicals Ltd.).

The aminoplast compound is not specifically limited so long as it has,per molecule, two or more methoxymethyl groups, and is exemplified bymelamine-based compound such as those named CYMEL Series that includehexamethoxymethylmelamine CYMEL (registered trademark) 303,tetrabutoxymethylglycoluril CYMEL 1170, tetramethoxymethylbenzoguanamineCYMEL 1123 (all from Nippon Cytec Industries, Ltd.); those named NIKALACSeries that include methylated melamine resin such as NIKALAC(registered trademark) MW-30HM, MW-390, MW-100LM, and MX-750LM, andmethylated urea resin such as NIKALAC MX-270, MX-280, and MX-290 (allfrom SANWA Chemical Co., Ltd.).

The polyfunctional oxetane compound is not specifically limited so longas it has, per molecule, two or more oxetanyl groups, and is exemplifiedby OXT-221, OX-SQ-H, and OX-SC (all from Toagosei Co., Ltd.) thatcontain oxetanyl group.

The phenoplast compound has two or more hydroxymethyl groups permolecule, and causes, when exposed high temperatures during thermalcuring, a crosslinking reaction based on dehydration condensation withthe crosslinking group of the triazine ring-containing polymer of thepresent invention to proceed.

The phenoplast compound is exemplified by2,6-dihydroxymethyl-4-methylphenol, 2,4-dihydroxymethyl-6-methylphenol,bis(2-hydroxy-3-hydroxymethyl-5-methylphenyl)methane,bis(4-hydroxy-3-hydroxymethyl-5-methylphenyl)methane,2,2-bis(4-hydroxy-3,5-dihydroxymethylphenyl)propane,bis(3-formyl-4-hydroxyphenyl)methane,bis(4-hydroxy-2,5-dimethylphenyl)formylmethane, andα,α-bis(4-hydroxy-2,5-dimethylphenyl)-4-formyltoluene.

The phenoplast compound is also commercially available, and isspecifically exemplified by 26DMPC, 46DMOC, DM-BIPC-F, DM-BIOC-F,TM-BIP-A, BISA-F, BI25X-DF, and BI25X-TPA (all from Asahi YukizaiCorporation).

Among them, polyfunctional (meth)acrylic compound is preferred from theviewpoint of capability of suppressing decrease in the refractive indexdue to blending of the crosslinking agent, and of allowing rapidprogress of the curing reaction, and in particular, polyfunctional(meth)acrylic compound, shown below, having an isocyanuric acid skeletonis more preferred for its excellence in compatibility with the triazinering-containing polymer.

The polyfunctional (meth)acrylic compound having such skeleton isexemplified by NK Ester A-9300 and NK Ester A-9300-1CL (both fromShin-Nakamura Chemical Co., Ltd.).

wherein each of R¹¹¹ to R¹¹³ independently represents a monovalentorganic group having at least one (meth)acrylic group at the terminal.

Also from the viewpoint of further improving the curing rate, andenhancing the solvent resistance, acid resistance, and alkali resistanceof the obtainable cured film, it is preferred to use polyfunctional(meth)acrylic compound that exists in a liquid form at 25° C., and has aviscosity of 5,000 mPa·s or lower, preferably 1 to 3,000 mPa·s, morepreferably 1 to 1,000 mPa·s, and even more preferably 1 to 500 mPa s(referred to as low viscosity crosslinking agent, hereinafter)independently, or by combining two or more kinds of them, or bycombining it with the aforementioned polyfunctional (meth)acryliccompound having an isocyanuric acid skeleton.

Also this sort of low-viscosity crosslinking agent is commerciallyavailable, and from among the aforementioned polyfunctional(meth)acrylic compounds, typically exemplified are crosslinking agentshaving a relatively long chain between (meth)acrylic groups, such as NKester A-GLY-3E (85 mPa·s, 25° C.), A-GLY-9E (95 mPa·s, 25° C.),A-GLY-20E (200 mPa·s, 25° C.), A-TMPT-3EO (60 mPa·s, 25° C.),A-TMPT-9EO, ATM-4E (150 mPa·s, 25° C.), and ATM-35E (350 mPa·s, 25° C.)(all from Shin-Nakamura Chemical Co., Ltd.).

In further consideration of also improving the alkali resistance of theobtainable cured film, preferred is use of at least either NK esterA-GLY-20E (from Shin Nakamura Chemical Co., Ltd.) or ATM-35E (from ShinNakamura Chemical Co., Ltd.), in combination with the polyfunctional(meth)acrylic compound having an isocyanuric acid skeleton.

In an additional case where a film formed of the triazinering-containing polymer of the present invention is stacked on aprotective film typically formed of PET or polyolefin and intended forphoto-irradiation through the protective film, good curability of thefilm stacked film is obtainable without being affected by oxygeninhibition. Since the protective film needs to be peeled off after thecuring, so that preferred is use of polybasic acid-modified acrylicoligomer that gives an easy-peel film.

The aforementioned crosslinking agents may be used independently, or bycombining two or more kinds of them. The amount of consumption of thecrosslinking agent is preferably 1 to 100 parts, per 100 parts by massof the triazine ring-containing polymer, wherein considering the solventresistance, the lower limit thereof is preferably 2 parts by mass, andmore preferably 5 parts by mass, meanwhile again consideringcontrollability of the refractive index, the upper limit thereof ispreferably 20 parts by mass, and more preferably 15 parts by mass.

The composition of the present invention may also be blended with aninitiator suited to each crosslinking agent. Note in a case where thepolyfunctional epoxy compound and/or the polyfunctional (meth)acryliccompound is used as the crosslinking agent, an initiator may be used,although the photo-curing can proceed to give a cured film even withoutthe initiator, as described previously.

In a case where the polyfunctional epoxy compound is used as thecrosslinking agent, a photoacid generator or a photobase generator maybe used.

The photoacid generator may only be properly selectable from known onesfor use, for which onium salt derivatives such as diazonium salt,sulfonium salt and iodonium salt may be typically used.

Specific examples thereof include aryl diazonium salt such as phenyldiazonium hexafluorophosphate, 4-methoxyphenyldiazoniumhexafluoroantimonate, and 4-methylphenyldiazonium hexafluorophosphate;diaryliodonium salt such as diphenyliodonium hexafluoroantimonate,di(4-methylphenyl)iodonium hexafluorophosphate, anddi(4-tert-butylphenyl)iodonium hexafluorophosphate; and triarylsulfoniumsalt such as triphenylsulfonium hexafluoroantimonate,tris(4-methoxyphenyl)sulfonium hexafluorophosphate,diphenyl-4-thiophenoxyphenylsulfonium hexafluoroantimonate,diphenyl-4-thiophenoxyphenylsulfonium hexafluorophosphate,4,4′-bis(diphenylsulfonio)phenylsulfide bishexafluoroantimonate,4,4′-bis(diphenylsulfonio)phenylsulfide bishexafluorophosphate,4,4′-bis[di(B-hydroxyethoxy)phenylsulfonio]phenyl sulfidebishexafluoroantimonate,4,4′-bis[di(B-hydroxyethoxy)phenylsulfonio]phenyl sulfidebishexafluorophosphate,4-[4′-(benzoyl)phenylthio]phenyl-di(4-fluorophenyl)sulfoniumhexafluoroantimonate and4-[4′-(benzoyl)phenylthio]phenyl-di(4-fluorophenyl)sulfoniumhexafluorophosphate.

These onium salts may be commercially available, and is specificallyexemplified by Sun-Aid SI-60, SI-80, SI-100, SI-60L, SI-80L, SI-100L,SI-L145, SI-L150, SI-L160, SI-L110 and SI-L147 (all from SanshinChemical Industry Co., Ltd.); UVI-6950, UVI-6970, UVI-6974, UVI-6990,UVI-6992 (all from Union Carbide Corporation); CPI-100P, CPI-100A,CPI-200K and CPI-200S (all from San-Apro Ltd.); Adeka Optomer SP-150,SP-151, SP-170 and SP-171 (all from ADEKA Corporation); Irgacure 261(from BASF SE); CI-2481, CI-2624, CI-2639 and CI-2064 (all from NipponSoda Co., Ltd.); CD-1010, CD-1011 and CD-1012 (all from Sartomer);DS-100, DS-101, DAM-101, DAM-102, DAM-105, DAM-201, DSM-301, NAI-100,NAI-101, NAI-105, NAI-106, SI-100, SI-101, SI-105, SI-106, PI-105,NDI-105, BENZOIN TOSYLATE, MBZ-101, MBZ-301, PYR-100, PYR-200, DNB-101,NB-101, NB-201, BBI-101, BBI-102, BBI-103 and BBI-109, (all from MidoriKagaku Co., Ltd.); PCI-061T, PCI-062T, PCI-020T and PCI-022T (all fromNippon Kayaku Co., Ltd.); and IBPF and IBCF (from SANWA Chemical Co.,Ltd.).

On the other hand, also the photobase generator may only be properlyselectable from known ones for use, for which Co-amine complex-based,oxime carboxylate ester-based, carbamate ester-based, and quaternaryammonium salt-based photobase generators may be used.

Specific examples thereof include 2-nitrobenzylcyclohexyl carbamate,triphenylmethanol, O-carbamoylhydroxylamide, 0-carbamoyloxime,[[(2,6-dinitrobenzyl)oxy]carbonyl]cyclohexylamine,bis[[(2-nitrobenzyl)oxy]carbonyl]hexane-1,6-diamine,4-(methylthiobenzoyl)-1-methyl-1-morpholinoethane,(4-morpholinobenzoyl)-1-benzyl-1-dimethylaminopropane,N-(2-nitrobenzyloxycarbonyl)pyrrolidine, hexaamminecobalt(III)tris(triphenylmethylborate),2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone,2,6-dimethyl-3,5-diacetyl-4-(2′-nitrophenyl)-1,4-dihydropyridine, and2,6-dimethyl-3,5-diacetyl-4-(2′,4′-dinitrophenyl)-1,4-dihydropyridine.Alternatively, the photobase generator may be commercially available,and is specifically exemplified by TPS-OH, NBC-101 and ANC-101 (all fromMidori Kagaku Co., Ltd.).

The amount of consumption of the photoacid or photobase generator, whenused, is preferably in the range from 0.1 to 15 parts by mass, per 100parts by mass of the polyfunctional epoxy compound, and more preferablyin the range from 1 to 10 parts by mass.

Optionally, 1 to 100 parts by mass of an epoxy resin curing agent may beblended per 100 parts by mass of the polyfunctional epoxy compound.

Meanwhile, in a case where the polyfunctional (meth)acrylic compound isused, a photoradical polymerization initiator may be used.

Also the photoradical polymerization initiator may only be properlyselectable from known ones for use, and is exemplified by acetophenones,benzophenones, Michler's benzoyl benzoates, amyloxime esters, oximeesters, tetramethylthiuram monosulfide, and thioxanthones.

In particular, preferred is a photo-cleavable photoradicalpolymerization initiator. The photocleavable photoradical polymerizationinitiator has been described in “Saishin UV Koka Gijutu (in Japanese,Latest UV Curing Technology) (p. 159, issued by: Kazuhiro Takausu,published by: Technical Information Institute Co., Ltd., 1991).

Commercially available photoradical polymerization initiator isexemplified by Irgacure (trade name) 127, 184, 369, 379, 379EG, 651,500, 754, 819, 903, 907, 784, 2959, CGI1700, CGI1750, CGI1850, CG24-61,OXE01, OXE02, Darocur 1116, 1173 and MBF from BASF; Lucirin (trade name)TPO from BASF; Ebecryl P36 from UCB Inc.; Esacure (trade name) KIP150,KIP65LT, KIP100F, KT37, KT55, KT046 and KIP75/B from Fratelli LambertiS.p.A.

The amount of consumption of the photoradical polymerization initiator,when used, is preferably in the range from 0.1 to 200 parts by mass, per100 parts by mass of the polyfunctional (meth)acrylate compound, andmore preferably in the range from 1 to 150 parts by mass.

To the composition of the present invention, a polyfunctional thiolcompound having two or more mercapto groups per molecule may further beadded, typically for the purpose of promoting the reaction between thetriazine ring-containing polymer and the crosslinking agent.

More specifically, preferred is a polyfunctional thiol compoundrepresented by the formula below.

L represents a divalent to tetravalent organic group, and is preferablya divalent to tetravalent aliphatic group having 2 to 12 carbon atoms,or a divalent to tetravalent heterocyclic ring-containing group; and ismore preferably a divalent to tetravalent aliphatic group having 2 to 8carbon atoms, or a trivalent group having an isocyanuric acid skeleton(1,3,5-triazine-2,4,6-(1H,3H,5H)-trione ring) represented by the formulabelow.

n represents an integer of 2 to 4 corresponding to the valence of L.

wherein “.” represents a site of bonding with an oxygen atom.

The compound is specifically exemplified by1,4-bis(3-mercaptobutyryloxy)butane,1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione,pentaerythritol tetrakis(3-mercaptobutyrate), trimethylolpropanetris(3-mercaptobutyrate), and trimethylolethanetris(3-mercaptobutyrate).

These polyfunctional thiol compounds are also commercially available,and are exemplified by Karenz MT BD1, Karenz MT NR1, Karenz MT PE1, TPMBand TEMB (all from Showa Denko K.K.).

These polyfunctional thiol compounds may be used independently, or bycombining two or more kinds of them.

Although the amount of addition of the polyfunctional thiol compound,when used, is not particularly limited so long as it would not adverselyaffect the obtainable film, the amount in the present invention ispreferably 0.01 to 10% by mass, per 100% by mass of the solid content,and more preferably 0.03 to 6% by mass.

The composition of the present invention is preferably used after addingvarious solvent to dissolve therein the triazine ring-containingpolymer.

The solvent is exemplified by water, toluene, p-xylene, o-xylene,m-xylene, ethylbenzene, styrene, ethylene glycol dimethyl ether,propylene glycol monomethyl ether, ethylene glycol monomethyl ether,propylene glycol, propylene glycol monoethyl ether, ethylene glycolmonoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycolmethyl ether acetate, propylene glycol monomethyl ether acetate,ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether,propylene glycol monobutyl ether, ethylene glycol monobutyl ether,diethylene glycol diethyl ether, dipropylene glycol monomethyl ether,diethylene glycol monomethyl ether, dipropylene glycol monoethyl ether,diethylene glycol monoethyl ether, triethylene glycol dimethyl ether,diethylene glycol monoethyl ether acetate, diethylene glycol, 1-octanol,ethylene glycol, hexylene glycol, trimethylene glycol,1-methoxy-2-butanol, cyclohexanol, diacetone alcohol, furfuryl alcohol,tetrahydrofuryl alcohol, propylene glycol, benzyl alcohol,1,3-butanediol, 1,4-butanediol, 2,3-butanediol, y-butyrolactone,acetone, methyl ethyl ketone, methyl isopropyl ketone, diethyl ketone,methyl isobutyl ketone, methyl normal butyl ketone, cyclopentanone,cyclohexanone, ethyl acetate, isopropyl acetate, normal propyl acetate,isobutyl acetate, normal butyl acetate, ethyl lactate, methanol,ethanol, isopropanol, tert-butanol, allyl alcohol, normal propanol,2-methyl-2-butanol, isobutanol, normal butanol, 2-methyl-1-butanol,1-pentanol, 2-methyl-1-pentanol, 2-ethylhexanol, 1-methoxy-2-propanol,tetrahydrofuran, 1,4-dioxane, N,N-dimethylformamide,N,N-dimethylacetamide (DMAc), N-methylpyrrolidone, 1,3dimethyl-2-imidazolidinone, dimethylsulfoxide, andN-cyclohexyl-2-pyrrolidinone. All of them may be used independently, orby combining two or more kinds of them.

The triazine ring-containing polymer of the present invention excels insolubility in the organic solvent as described previously, and is highlysoluble in glycol ester-based solvent such as ethylene glycol monomethylether acetate, propylene glycol monomethyl ether acetate, diethyleneglycol monobutyl ether acetate, and diethylene glycol monoethyl etheracetate; ketone-based solvent such as acetone, methyl ethyl ketone,methyl isobutyl ketone, diisobutyl ketone, cyclopentanone,cyclohexanone, and diacetone alcohol; and ester-based solvents such asethyl acetate, methyl acetate, butyl acetate, methoxybutyl acetate,cellosolve acetate, amyl acetate, normal propyl acetate, isopropylacetate, methyl lactate, ethyl lactate, and butyl lactate. The triazinering-containing polymer is therefore particularly preferred for formingthe film at a site where any of these solvents is required.

The solid concentration in the composition in this case is notspecifically limited so long as it would not affect the shelf stability,and may only be determined suitably depending on desired thickness ofthe film. More specifically, the solid content is preferably 0.1 to 50%by mass from the viewpoint of solubility and shelf stability, and ismore preferably 0.1 to 40% by mass.

The composition of the present invention may contain any ingredientother than the triazine ring-containing polymer, the crosslinking agentand the solvent, which may typically be additives such as levelingagent, surfactant, and silane coupling agent, so long as the effect ofthe present invention will not be undermined.

The surfactant is exemplified by polyoxyethylene alkyl ether such aspolyoxyethylene lauryl ether, polyoxyethylene stearyl ether,polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether;polyoxyethylene alkyl allyl ethers such as polyoxyethylene octylphenolether and polyoxyethylene nonylphenol ether;polyoxyethylene-polyoxypropylene block copolymers; sorbitan fatty acidesters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitanmonostearate, sorbitan monooleate, sorbitan trioleate and sorbitantristearate; nonionic surfactants such as polyoxyethylene sorbitanmonolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylenesorbitan monostearate, polyoxyethylene sorbitan trioleate andpolyoxyethylene sorbitan tristearate; fluorine-containing surfactantsunder trade names of EFTOP EF301, EF303 and EF352 (from MitsubishiMaterials Electronic Chemicals Co., Ltd., formerly Gemco Inc.)),Megaface F171, F173, R-08, R-30, R-40, F-553, F-554, RS-75 and RS-72K(from DIC Corporation), Fluorad FC430 and FC431 (from Sumitomo 3MLimited), AsahiGuard AG 710, Surflon S-382, SC101, SC102, SC103, SC104,SC105 and SC106 (from AGC Inc.); and organosiloxane polymers KP341 (fromShin-Etsu Chemical Co., Ltd), BYK-302, BYK-307, BYK-322, BYK-323,BYK-330, BYK-333, BYK-370, BYK-375 and BYK-378 (from BYK Japan KK).

These surfactants may be used independently, or by combining two or morekinds of them. The amount of consumption of the surfactant is preferably0.0001 to 5 parts by mass, per 100 parts by mass of the triazinering-containing polymer, more preferably 0.001 to 1 part by mass, andeven more preferably 0.01 to 0.5 parts by mass.

The film-forming composition of the present invention may be applied toa base, optionally followed by heating to evaporate the solvent off, andthen may be heated or irradiated with light to form a desired curedfilm.

Method for applying the composition is freely selectable, for whichemployable is any of methods including spin coating, dipping, flowcoating, ink-jetting, jet dispensing, spraying, bar coating, gravurecoating, slit coating, roll coating, transfer printing, brush coating,blade coating, and air knife coating.

The base is exemplified by those formed of silicon, glass with indiumtin oxide (ITO) film formed thereon, glass with indium zinc oxide (IZO)film formed thereon, metal nanowire, polyethylene terephthalate (PET),plastic, glass, quartz, and ceramic. Also flexible base havingflexibility is employable.

Temperature of baking for evaporating off the solvent is typically, butnot specifically limited to, 110 to 400° C.

Method for the baking is typically, but not specifically limited to,evaporation with use of a hot plate or an oven, under an appropriateatmosphere such as the ambient air, inert gas such as nitrogen, orvacuum.

The temperature and time of the baking may only be suitably selectedaccording to processes for obtaining desired electronic device, that is,the baking condition is selectable so that the physical values of theresulting film conform to the required characteristics of the electronicdevice.

Also conditions for photo-irradiation are not specifically limited, forwhich any appropriate energy and time of irradiation are used, dependingon the triazine ring-containing polymer and the crosslinking agent to beemployed.

The film and cured film obtained as described above can achieve highheat resistance, high refractive index and low volume shrinkage, and aretherefore suitably applicable to the fields of electronic devices andoptical materials, when manufacturing a part of liquid crystal display,organic EL element (organic EL display or organic EL lighting), touchpanel, optical semiconductor (LED) element, solid-state image sensor,organic thin-film solar cell, dye-sensitized solar cell, organicthin-film transistor (TFT), lens, prism, camera, binoculars, microscope,semiconductor exposure apparatus, and the like.

In particular, the film and cured film formed of the composition of thepresent invention demonstrates high transparency and high refractiveindex, and can therefore improve when applied to a planarization layeror a light scattering layer of organic EL lighting, the light extractionefficiency (light diffusion efficiency) and the durability thereof.

When using the composition of the present invention for the lightscattering layer of organic EL lighting, any of known light diffusingagents may be used without special limitation. They may be usedindependently, two or more kinds of them in the same category may becombined for use, or two or more kinds of them in different categoriesmay be combined for use.

Examples of the light diffusing agent include organic light diffusingagent or the like.

The organic light diffusing agent is exemplified by crosslinkedpoly(methyl methacrylate) (PMMA) particle, crosslinked poly(methylacrylate) particle, crosslinked polystyrene particle, crosslinkedstyrene acrylic copolymer particle, melamine-formaldehyde particle,silicone resin particle, silica-acrylic composite particle, nylonparticle, benzoguanamine-formaldehyde particle,benzoguanamine-melamine-formaldehyde particle, fluororesin particle,epoxy resin particle, polyphenylene sulfide resin particle,polyethersulfone resin particle, polyacrylonitrile particle, andpolyurethane particle.

These light diffusing agents may be surface-treated with an appropriatesurface modifier.

EXAMPLES

The present invention will be described more specifically referring toExamples and Comparative Examples, where the present invention is notlimited to the Examples below. The measurement apparatuses used inExamples are as follows.

[¹H-NMR]

Apparatus: Bruker NMR System AVANCE III HD 500 (500 MHz)

Measuring solvent: DMSO-d6

Reference material: tetramethylsilane (TMS) (δ0.0 ppm)

[GPC]

Apparatus: HLC-8200 GPC, from Tosoh Corporation

Column: Tosoh TSKgel α-3000+Tosoh TSKgel α-4000

Column temperature: 40° C.

Solvent: dimethylformamide (DMF)

Detector: UV (271 nm)

Calibration curve: standard polystyrene

[Ellipsometer]

Apparatus: multi-incident angle spectroscopic ellipsometer VASE, fromJ.A. Woollam Japan Corporation

[Spectrophotometric Colorimeter]

Apparatus: CM-3700 A, from Konica Minolta, Inc.

[Optical Microscope]

Apparatus: OLYMPUS BX 51, from Olympus Corporation

[Ultraviolet-Visible-Near Infrared Spectrophotometer]

Apparatus: V-670, from JASCO Corporation

[1] Synthesis of Triazine Ring-Containing Polymer [Example 1-1]Synthesis of Polymer Compound [4]

Into a 1,000 mL four-necked flask, placed were 1,3-phenylenediamine [2](35.18 g, 0.325 mol, from Amino-Chem Co., Ltd.) and 666.3 g ofdimethylacetamide (DMAc, from Kanto Chemical Co., Inc.), the inside ofthe flask was replaced with nitrogen, and the content was stirred todissolve 1,3-phenylenediamine [2] in DMAc. The content was then cooledon an ethanol-dry ice bath down to −10° C., to which2,4,6-trichloro-1,3,5-triazine [1] (60.0 g, 0.325 mol, from TokyoChemical Industry Co., Ltd.) was added while monitoring so that theinternal temperature would not reach or exceed 0° C. After 30-minutestirring, the reaction liquid was heated on an oil bath preset at 90 to100° C., so as to elevate the inner temperature to 85° C.±5° C. Afterone-hour stirring at an internal temperature of 85° C.,2-(4-aminophenyl)ethanol [3] (53.56 g, 0.456 mol, from OakwoodCorporation), preliminarily dissolved in 107.12 g of DMAc, was addeddropwise, and the content was stirred for 3 hours. Thereafter,2-aminoethanol (59.62 g, from Tokyo Chemical Industry Co., Ltd.) wasadded dropwise, the content was cooled down to room temperature, stirredfor 30 minutes, and the stirring was stopped. THF (491 g), ammoniumacetate (442 g) and ion-exchanged water (442 g) were added to thereaction liquid, and the content was stirred for 30 minutes. Afterstopping the stirring, the liquid was transferred to a separatingfunnel, separated into an organic layer and an aqueous layer, and theorganic layer was collected. The collected organic layer was addeddropwise to a mixed solution of methanol (491 g) and ion-exchanged water(1,964 g), to cause reprecipitation. The resulted precipitate wascollected by filtration, and dried in a vacuum dryer at 120° C. for 8hours, to obtain 78.5 g of a desired polymer compound [4] (referred toas P-1, hereinafter). The measurement result of ¹H-NMR spectrum of thecompound P-1 is illustrated in FIG. 1 .

The weight average molecular weight Mw of the compound P-1 in terms ofpolystyrene, measured by GPC, was found to be 6,070, and thepolydispersity Mw/Mn was found to be 2.6.

[Example 1-2] Synthesis of Polymer Compound [5]

Into a 150 mL four-necked flask, placed were 25.0 g of the compound P-1synthesized in Example 1-1, 100.0 g of THF (from Junsei Chemical Co.,Ltd.), and 11.66 g of pure water, the inside of the flask was replacedwith nitrogen, and the content was stirred to dissolve P-1 in THF. Thecontent was then heated so as to elevate the inner temperature to 60°C., to which 12.70 g of 2-isocyanatoethyl acrylate (Karenz AOI, fromShowa Denko K.K.) was added, and the content was stirred for 3 hours.Then, after cooling down to room temperature, the reaction liquid wasadded dropwise into a mixed solution of methanol (149 g) andion-exchanged water (448 g), to cause reprecipitation. The resultedprecipitate was collected by filtration, and dried in a vacuum dryer at80° C. for 3 hours, to obtain 21.6 g of a desired polymer compound [5](referred to as P-2, hereinafter). The measurement result of ¹H-NMRspectrum of the compound P-2 is illustrated in FIG. 2 .

The weight average molecular weight Mw of the compound P-2 in terms ofpolystyrene, measured by GPC, was found to be 6,250, and thepolydispersity Mw/Mn was found to be 3.3.

[Example 1-3] Synthesis of Polymer Compound [7]

Into a 500 mL four-necked flask, placed were 1,3-phenylenediamine [2](11.73 g, 0.108 mol, from Amino-Chem Co., Ltd.) and 204.96 g ofdimethylacetamide (DMAc, from Kanto Chemical Co., Inc.), the inside ofthe flask was replaced with nitrogen, and the content was stirred todissolve 1,3-phenylenediamine [2] in DMAc. The content was then cooledon an ethanol-dry ice bath down to −10° C., to which2,4,6-trichloro-1,3,5-triazine [1] (20.00 g, 0.108 mol, from TokyoChemical Industry Co., Ltd.) was added while monitoring so that theinternal temperature would not reach or exceed 0° C. After 30-minutestirring the reaction liquid, 87.8 g of DMAc was added to a 500 mLfour-necked flask in advance, and after nitrogen replacement and aftersetting the oil bath at 90 to 100° C., the reaction liquid was addeddropwise into the 500 mL four-necked flask, while keeping the internaltemperature at 85° C.±5° C. After one-hour stirring at an internaltemperature of 85° C., aniline [6] (10.10 g, 0.108 mol, from TokyoChemical Industry Co., Ltd.) and 2-(4-aminophenyl)ethanol [3] (104.14 g,0.759 mol, from Sugai Chemical Ind. Co., Ltd.), preliminarily dissolvedin 208.29 g of DMAc, were added dropwise, and the content was stirredfor 3 hours. Three hours after, acrylic acid chloride (14.72 g, 0.163mol, from Tokyo Chemical Industry Co., Ltd.) was added dropwise, and thecontent was stirred for additional 30 minutes. Thereafter, the contentwas cooled down to 60° C., triethylamine (54.87 g, 0.542 mol, from TokyoChemical Industry Co., Ltd.) was added dropwise, the content was stirredfor 30 minutes, and the stirring was stopped. The reaction solution wasthen mixed with ion-exchanged water (188.6 g) to which 188.6 g ofammonium acetate was preliminarily added and THF (210 g), and thecontent was stirred for 30 minutes. After stopping the stirring, theliquid was transferred to a separating funnel, separated into an organiclayer and an aqueous layer, and the organic layer was collected. Thecollected organic layer was added dropwise into a mixed solution ofmethanol (251 g) and ion-exchanged water (629 g), to causereprecipitation. The resulted precipitate was collected by filtration,and dried in a vacuum dryer at 120° C. for 8 hours, to obtain 31.0 g ofa desired polymer compound [7] (referred to as P-3, hereinafter). Themeasurement result of ¹H-NMR spectrum of the compound P-3 is illustratedin FIG. 3 .

The weight average molecular weight Mw of the compound P-3 in terms ofpolystyrene, measured by GPC, was found to be 7,270, and thepolydispersity Mw/Mn was found to be 3.3.

[Comparative Example 1-1] Synthesis of Polymer Compound [8]

According to the synthesis method described in WO 2010/128661, a polymercompound [8] (referred to as P-4, hereinafter) was synthesized.

The measurement result of ¹H-NMR spectrum of the compound P-4 isillustrated in FIG. 4 .

The weight average molecular weight Mw of the compound P-4 in terms ofpolystyrene, measured by GPC, was found to be 11,580, and thepolydispersity Mw/Mn was found to be 3.7.

[Comparative Example 1-2] Synthesis of Polymer Compound [9]

According to the synthesis method described in WO 2013/094663, a polymercompound [9] (referred to as P-5, hereinafter) was synthesized.

The measurement result of ¹H-NMR spectrum of the compound P-5 isillustrated in FIG. 5 .

The weight average molecular weight Mw of the compound P-5 in terms ofpolystyrene, measured by GPC, was found to be 6,182, and thepolydispersity Mw/Mn was found to be 5.8.

[Example 1-4] Synthesis of Polymer Compound [10]

Into a 1,000 mL four-necked flask, placed were 1,3-phenylenediamine [2](42.22 g, 0.390 mol, from Amino-Chem Co., Ltd.) and 672.62 g ofdimethylacetamide (DMAc, from Kanto Chemical Co., Inc.), the inside ofthe flask was replaced with nitrogen, and the content was stirred todissolve 1,3-phenylenediamine [2] in DMAc. The content was then cooledon an ethanol-dry ice bath down to −10° C., to which2,4,6-trichloro-1,3,5-triazine [1] (60.00 g, 0.325 mol, from TokyoChemical Industry Co., Ltd.) was added while monitoring so that theinternal temperature would not reach or exceed 0° C. After 30-minutestirring, the reaction liquid was heated on an oil bath preset at 90 to100° C., so as to elevate the inner temperature to 85° C.±5° C. Afterone-hour stirring at an internal temperature of 85° C., aniline [6](18.18 g, 0.195 mol, from Tokyo Chemical Industry Co., Ltd.) and2-(4-aminophenyl)ethanol [3] (26.78 g, 0.195 mol, from Oakwood Products,Inc.), preliminarily dissolved in 42.93 g of DMAc, were added dropwise,and the content was stirred for 3 hours. Thereafter, 2-aminoethanol(59.62 g, from Tokyo Chemical Industry Co., Ltd.) was added dropwise,the content was cooled down to room temperature, stirred for 30 minutes,and the stirring was stopped. THF (369 g), ammonium acetate (415 g) andion-exchanged water (415 g) were added to the reaction liquid, and thecontent was stirred for 30 minutes. After stopping the stirring, theliquid was transferred to a separating funnel, separated into an organiclayer and an aqueous layer, and the organic layer was collected. Thecollected organic layer was added dropwise to a mixed solution ofmethanol (461 g) and ion-exchanged water (1,845 g), to causereprecipitation. The resulted precipitate was collected by filtration,and dried in a vacuum dryer at 120° C. for 8 hours, to obtain 89.3 g ofa desired polymer compound [10] (referred to as P-6, hereinafter). Themeasurement result of ¹H-NMR spectrum of the compound P-6 is illustratedin FIG. 6 .

The weight average molecular weight Mw of the compound P-6 in terms ofpolystyrene, measured by GPC, was found to be 23,350, and thepolydispersity Mw/Mn was found to be 6.5.

[2] Preparation of Crosslinking Agent-Added Film-Forming Composition,and Formation of Cured Film Example 2-1

P-1 (2.40 g) obtained in Example 1-1 was dissolved in cyclopentanone(abbreviated as CPN, hereinafter) (5.60 g), to which 0.80 g ofcrosslinking agent ATM-35E (from Shin Nakamura Chemical Co., Ltd.) inthe form of 30% mass solution in CPN and 0.80 g of crosslinking agentDN-0075 (from Nippon Kayaku Co., Ltd.) in the form of 30% by masssolution in CPN, 1.2 g of photoradical polymerization initiator Omnirad2959 (from IGM Resins B.V.) in the form of 10% by mass solution in CPN,0.24 g of surfactant Megaface R-40 (from DIC Corporation) in the form of1% by mass solution in CPN, and 8.97 g of CPN were added, whosesolubilization was visually confirmed, whereby a varnish having a solidcontent of 15% by mass (referred to as SP-1 solution, hereinafter) wasprepared.

The SP-1 solution was spin-coated over a 50 mm×50 mm×0.7 mm thickalkali-free glass substrate with use of a spin coater at 200 rpm for 5seconds, and then at 1,000 rpm for 30 seconds, pre-dried at 100° C. forone minute on a hot plate, and then irradiated with light of 365 nmwavelength with use of a UV irradiation apparatus at an exposure dose of400 mJ/cm², to obtain a cured film (referred to as SP-1 film,hereinafter).

Example 2-2

P-2 (1.20 g) obtained in Example 1-2 was dissolved in CPN (2.80 g), towhich 0.24 g of crosslinking agent ATM-35E (from Shin Nakamura ChemicalCo., Ltd.) in the form of 50% mass solution in CPN, 0.24 g ofcrosslinking agent DN-0075 (from Nippon Kayaku Co., Ltd.) in the form of50% by mass solution in CPN, 0.6 g of photoradical polymerizationinitiator Omnirad 2959 (from IGM Resins B.V.) in the form of 10% by masssolution in CPN, 0.012 g of surfactant Megaface R-40 (from DICCorporation) in the form of 10% by mass solution in CPN, and 4.91 g ofCPN were added, whose solubilization was visually confirmed, whereby avarnish having a solid content of 15% by mass (referred to as SP-2solution, hereinafter) was prepared.

With use of such SP-2 solution, a cured film (referred to as SP-2 film,hereinafter) was obtained according to the same procedure as in Example2-1.

Example 2-3

P-3 (2.40 g) obtained in Example 1-3 was dissolved in CPN (5.60 g), towhich 0.80 g of crosslinking agent ATM-35E (from Shin Nakamura ChemicalCo., Ltd.) in the form of 30% mass solution in CPN, 0.80 g ofcrosslinking agent DN-0075 (from Nippon Kayaku Co., Ltd.) in the form of30% by mass solution in CPN, 1.2 g of photoradical polymerizationinitiator Omnirad 2959 (from IGM Resins B.V.) in the form of 10% by masssolution in CPN, 0.24 g of surfactant Megaface R-40 (from DICCorporation) in the form of 1% by mass solution in CPN, and 8.97 g ofCPN were added, whose solubilization was visually confirmed, whereby avarnish having a solid content of 15% by mass (referred to as SP-3solution, hereinafter) was prepared.

With use of such SP-3 solution, a cured film (referred to as SP-3 film,hereinafter) was obtained according to the same procedure as in Example2-1.

Comparative Example 2-1

P-4 (1.20 g) obtained in Comparative Example 1-1 was dissolved in CPN(4.80 g), to which 0.40 g of crosslinking agent ATM-35E (from ShinNakamura Chemical Co., Ltd.) in the form of 30% mass solution in CPN,0.44 g of crosslinking agent DN-0075 (from Nippon Kayaku Co., Ltd.) inthe form of 30% by mass solution in CPN, 0.60 g of photoradicalpolymerization initiator Omnirad 2959 (from IGM Resins B.V.) in the formof 10% by mass solution in CPN, 0.12 g of surfactant Megaface R-40 (fromDIC Corporation) in the form of 1% by mass solution in CPN, and 2.49 gof CPN were added, whose solubilization was visually confirmed, wherebya varnish having a solid content of 15% by mass (referred to as SP-4solution, hereinafter) was prepared.

With use of such SP-4 solution, a cured film (referred to as SP-4 film,hereinafter) was obtained according to the same procedure as in Example2-1.

Comparative Example 2-2

P-5 (2.50 g) obtained in Comparative Example 1-2 was dissolved in CPN(5.83 g), to which 0.71 g of blocked isocyanate (BI7992, 1,500 mPa·s,from Baxenden Chemicals, Ltd.), as a crosslinking agent, in the form of70% by mass solution in PGME (propylene glycol monomethyl ether), 0.25 gof surfactant Megaface R-40 (from DIC Corporation) in the form of 1% bymass solution in CPNA, and 9.76 g of CPN were added, whosesolubilization was visually confirmed, whereby a varnish having a solidcontent of 15% by mass (referred to as SP-5 solution, hereinafter) wasprepared.

With use of such SP-5 solution, a cured film (referred to as SP-5 film,hereinafter) was obtained according to the same procedure as in Example2-1.

[Measurement of Solvent Resistance (Crack Resistance) and Transmittance]

The substrate with the cured film formed above was set on a spin coater,and thereon 1 ml of CPN was coated. Next, the cured film was exposed tothe solvent under rotation at 50 rpm for 60 seconds, while preventingthe liquid from being scattered from the substrate. The substrate wasthen rotated at 1,000 rpm for 30 seconds to spin off the solvent. Thesubstrate was then dried on a hot plate at 120° C. for 10 seconds, andsubjected to measurement of the refractive index, film thickness,estimation of residual film ratio, and observation of the film surfaceunder an optical microscope.

The residual film ratio was estimated by the equation below.

Residual film ratio (%)=[(Film thickness after solvent exposure)/(Filmthickness before solvent exposure)]×100

Also the transmittance was measured before solvent exposure.

Measured results of the refractive index, film thickness, residual filmratio, and average transmittance at 300 to 800 nm are summarized inTable 1, micrographs of the surfaces of the cured films in Examples 2-1to 2-3 are shown in FIGS. 7 to 9 , and micrographs of the surfaces ofthe cured films in Comparative Examples 2-1 and 2-2 are shown in FIGS.10 and 11 .

TABLE 1 Comparative Comparative Example 2-1 Example 2-2 Example 2-3Example 2-1 Example 2-2 Before After Before After Before After BeforeAfter Before After solvent solvent solvent solvent solvent solventsolvent solvent solvent solvent exposure exposure exposure exposureexposure exposure exposure exposure exposure exposure Refractive 1.7261.726 1.690 1.690 1.702 1.703 1.725 Measurement 1.736 1.733 index not (@550) possible Thickness 907 902 873 862 900 891 1.225 939 942 (nm)Residual film — 99 — 99 — 99 90.4 — 100 ratio (%) Transmittance 91.3 —91.6 — 91.4 — 90.4 — 89.3 — (%)

The cured films (SP-1 to SP-3 films) in Examples 2-1 to 2-3 were foundto demonstrate high residual film ratio as judged from Table 1, andfound to cause neither surface roughness nor crack as judged from FIGS.7 to 9 , proving excellence in solvent resistance (crack resistance).

In contrast, the cured film in Comparative Example 2-1 (SP-4 film) wasfound to cause surface roughness and crack after exposed to the solventand dried on a hot plate at 120° C. for 10 seconds (see FIG. 10 ), andwas not in a condition suitable for measurement of the refractive indexand thickness.

The cured film (SP-5 film) in Comparative Example 2-2 was found to causeno surface roughness and crack, but was found to be lowered in thetransmittance than in Examples (see FIG. 11 ).

These results teach that the cured films formed of the polymer compoundsin Examples excel in solvent resistance (crack resistance) and opticalproperties, by virtue of the crosslinking moiety at the polymerterminal.

[Example 3-1] Synthesis of Polymer Compound [15]

Into a 3,000 mL four-necked flask, placed were2,2′-bis(trifluoromethyl)-4,4′-diamine diphenyl ether [12](218.79 g,0.651 mol, from Wuhan Sun-shine Chemical Co., Ltd.) and 1,693.96 g ofdimethylacetamide (DMAc, from Kanto Chemical Co., Inc.), the inside ofthe flask was replaced with nitrogen, and the content was stirred todissolve 2,2′-bis(trifluoromethyl)-4,4′-diamine diphenyl ether [12] inDMAc. The content was then cooled on an ethanol-dry ice bath down to−10° C., to which 2,4,6-trichloro-1,3,5-triazine [11] (120.00 g, 0.651mol, f rom Amino-Chem (HK) Co., Ltd.) was added while monitoring so thatthe internal temperature would not reach or exceed 0° C. After 30-minutestirring the reaction liquid, 1,693.96 g of DMAc was added to a 5,000 mLfour-necked flask in advance, and after nitrogen replacement and aftersetting the oil bath at 90 to 100° C., the reaction liquid was addeddropwise into the 5,000 mL four-necked flask, while keeping the internaltemperature at 75° C.±5° C. After one-hour stirring at an internaltemperature of 75° C., aniline [14] (73.39 g, 0.456 mol, from TokyoChemical Industry Co., Ltd.) and 2-(4-aminophenyl)ethanol [13] (62.49 g,0.456 mol, from Oakwood Products, Inc.), preliminarily dissolved in124.97 g of DMAc, were added dropwise, and the content was stirred for 3hours. The content was then cooled down to room temperature, to whichn-propylamine (115.39 g, from Tokyo Chemical Industry Co., Ltd.) wasadded dropwise, the content was stirred for 30 minutes, and the stirringwas stopped. THF (2,051 g), ammonium acetate (1,846 g) and ion-exchangedwater (1,846 g) were added to the reaction liquid, and the content wasstirred for 30 minutes. After stopping the stirring, the liquid wastransferred to a separating funnel, separated into an organic layer andan aqueous layer, and the organic layer was collected. The collectedorganic layer was added dropwise to a mixed solution of methanol (3,282g) and ion-exchanged water (8,206 g), to cause reprecipitation. Theresulted precipitate was collected by filtration, and dried in a vacuumdryer at 120° C. for 8 hours, to obtain 235.51 g of a desired polymercompound [15] (referred to as P-11, hereinafter). The measurement resultof ¹H-NMR spectrum of the compound P-11 is illustrated in FIG. 12 .

The weight average molecular weight Mw of the compound P-11 in terms ofpolystyrene, measured by GPC, was found to be 6,070, and thepolydispersity Mw/Mn was found to be 2.6.

[Example 3-2] Synthesis of Polymer Compound [16]

Into a 500 mL four-necked flask, placed were 30.0 g of the compound P-11synthesized in Example 3-1, 150.0 g of tetrahydrofuran (THF, from JunseiChemical Co., Ltd.), and 3.0 g of pure water, the inside of the flaskwas replaced with nitrogen, and the content was stirred to dissolve P-11in THF. The content was then heated so as to elevate the innertemperature to 60° C., to which 15.0 g of 2-isocyanatoethyl acrylate(Karenz AOI, from Showa Denko K.K.) was added, and the content wasstirred for 3 hours. Then, after cooling down to room temperature, thereaction liquid was added dropwise into a mixed solution of methanol(158 g) and ion-exchanged water (396 g), to cause reprecipitation. Theresulted precipitate was collected by filtration, and dried in a vacuumdryer at 80° C. for 8 hours, to obtain 16.8 g of a desired polymercompound [16](referred to as P-12, hereinafter). The measurement resultof ¹H-NMR spectrum of the compound P-12 is illustrated in FIG. 13 .

The weight average molecular weight Mw of the compound P-12 in terms ofpolystyrene, measured by GPC, was found to be 7,310, and thepolydispersity Mw/Mn was found to be 2.3.

[Comparative Example 3-1] Synthesis of Polymer Compound [19]

According to the synthesis method described in WO 2016/194926, a polymercompound [19] (referred to as P-13, hereinafter) was synthesized.

The measurement result of ¹H-NMR spectrum of the compound P-13 isillustrated in FIG. 14 .

The weight average molecular weight Mw of the compound P-13 in terms ofpolystyrene-equivalent value, measured by GPC, was found to be 11,580,and the polydispersity Mw/Mn was found to be 3.7.

Example 4-1

P-11 (2.50 g) obtained in Example 3-1 was dissolved in PGME (5.83 g), towhich 0.71 g of blocked isocyanate (BI7992, 1,500 mPa·s, from BaxendenChemicals, Ltd.), as a crosslinking agent, in the form of 70% by masssolution in PGME, 0.25 g of surfactant Megaface F-563 (from DICCorporation) in the form of 1% by mass solution in PGMEA, 0.71 g ofPGME, and 1.70 g of THFA (tetrahydrofurfuryl alcohol) were added, whosesolubilization was visually confirmed, whereby a varnish having a solidcontent of 30% by mass (referred to as SP-11 solution, hereinafter) wasprepared.

The SP-11 solution was spin-coated over a 50 mm×50 mm×0.7 mm thickalkali-free glass substrate with use of a spin coater at 200 rpm for 5seconds, and then at 1,000 rpm for 30 seconds, pre-dried at 100° C. forone minute on a hot plate, followed by main drying at 200° C. for 5minutes, to obtain a cured film (referred to as SP-11 film,hereinafter).

Comparative Example 4-1

P-13 (2.50 g) obtained in Comparative Example 3-1 was dissolved in CPN(5.83 g), to which 0.71 g of blocked isocyanate (BI7992, 1,500 mPa·s,from Baxenden Chemicals, Ltd.), as a crosslinking agent, in the form of70% by mass solution in PGME, 0.25 g of surfactant Megaface R-40 (fromDIC Corporation) in the form of 1% by mass solution in CPNA, and 9.76 gof CPN were added, whose solubilization was visually confirmed, wherebya varnish having a solid content of 15% by mass (referred to as SP-12solution, hereinafter) was prepared.

With use of such SP-12 solution, a cured film (referred to as SP-12film, hereinafter) was obtained according to the same procedure as inExample 4-1.

The cured films obtained above were measured regarding the refractiveindex, thickness and b*. Results are summarized in Table 2. Results ofobservation of the surfaces of the cured films under an opticalmicroscope are shown in FIGS. 15 and 16 .

TABLE 2 Comparative Example Example 4-1 4-1 Refractive index 1.62Measurement not (@550 nm) possible Thickness 3,880 (nm) b* 0.48

As summarized in Table 2, the film in Comparative Example 4-1 was foundto be thick, and cracked upon being obtained as a cured film (SP-12film) due to absence of the crosslinking moiety in the compound P-13(see FIG. 16 ), so that optical properties could not be measured. Incontrast, the cured film (SP-11 film) in Example 4-1 was found to excelin crack resistance, while keeping high refractive index and hightransparency, despite large thickness (see FIG. 15 ).

[Example 5-1] Synthesis of Polymer Compound [102]

Into a 500 mL four-necked flask, placed were P-1 [4] (29.20 g) obtainedin Example 1-1, and 174.84 g of cyclopentanone (CPN, from ZeonCorporation), the inside of the flask was replaced with nitrogen, andthe content was stirred for dissolution. The solution was then heated toan internal temperature of 60° C., to which 14.51 g of 2-isocyanatoethylacrylate [101] (AOI-VM, from Showa Denko K.K.) was added dropwise, thecontent was stirred at an internal temperature of 60° C.±5° C. for onehour, to prepare a 30% by mass polymer compound [102] solution in CPN(referred to as P-21 solution, hereinafter).

[Example 5-2] Synthesis of Polymer Compound [104]

Into a 3,000 mL four-necked flask, placed were 1,3-phenylenediamine [2](43.98 g, 0.407 mol, from Amino-Chem Co., Ltd.),2,2′-bis(trifluoromethyl)-4,4′-diamine diphenyl ether [103] (136.75 g,0.407 mol, from Wuhan Sun-shine Chemical Co., Ltd.), and 1,949.90 g ofdimethylacetamide (DMAc, from Kanto Chemical Co., Inc.), the inside ofthe flask was replaced with nitrogen, and the content was stirred todissolve 1,3-phenylenediamine [2] and2,2′-bis(trifluoromethyl)-4,4′-diamine diphenyl ether [103] in DMAc. Thecontent was then cooled on an ethanol-dry ice bath down to −10° C., towhich 2,4,6-trichloro-1,3,5-triazine [1] (150.00 g, 0.813 mol, fromTokyo Chemical Industry Co., Ltd.) was added while monitoring so thatthe internal temperature would not reach or exceed 0° C., and finallycleaned off with 114.70 g of dimethylacetamide (DMAc, from KantoChemical Co., Inc.). After 30-minute stirring, the reaction liquid washeated up to an internal temperature of 85° C.±5° C. After one-hourstirring, 2-(4-aminophenyl)ethanol [3] (133.90 g, 0.976 mol, fromOakwood Corporation), preliminarily dissolved in 229.40 g of DMAc (fromKanto Chemical Co., Inc.), was added dropwise, and the content wasstirred for 3 hours. 2-Aminoethanol (154.02 g, from Tokyo ChemicalIndustry Co., Ltd.) was then added dropwise, the content was stirred for30 minutes, and the stirring was stopped. THF (1,456 g), ammoniumacetate (1,311 g) and ion-exchanged water (1,311 g) were added to thereaction liquid, and the content was stirred for 30 minutes. Afterstopping the stirring, the liquid was transferred to a separatingfunnel, separated into an organic layer and an aqueous layer, and theorganic layer was collected. The collected organic layer was addeddropwise to methanol (1,748 g) and ion-exchanged water (4,369 g), tocause reprecipitation. The resulted precipitate was collected byfiltration, and dried in a vacuum dryer at 150° C. for 8 hours, toobtain 353.6 g of a desired polymer compound [104] (referred to as P-22,hereinafter).

The weight average molecular weight Mw of the compound P-22 in terms ofpolystyrene-equivalent value, measured by GPC, was found to be 8,083,and the polydispersity Mw/Mn was found to be 3.2. The measurement resultof ¹H-NMR spectrum of the compound P-22 is illustrated in FIG. 17 .

[Example 5-3] Synthesis of Polymer Compound [105]

Into a 300 mL four-necked flask, placed were P-22 (polymer compound[104]) (30.00 g) obtained in Example 5-2, and 93.60 g of cyclopentanone(CPN, from Zeon Corporation), the inside of the flask was replaced withnitrogen, and the content was stirred for dissolution. The content wasthen heated to an internal temperature of 60° C., to which 10.11 g of2-isocyanatoethyl acrylate (AOI-VM, from Showa Denko K.K.) was addeddropwise, the content was stirred at an internal temperature of 60°C.±5° C. for one hour, to prepare a 30% by mass polymer compound [105]solution in CPN (referred to as P-23 solution, hereinafter).

Example 6-1

P-21 solution (4.42 g) obtained in Example 5-1, 0.088 g of crosslinkingagent ATM-35E (from Shin Nakamura Chemical Co., Ltd.), 0.088 g ofcrosslinking agent DN-0075 (from Nippon Kayaku Co., Ltd.), 0.053 g ofphotoradical polymerization initiator Omnirad 2959 (from IGM ResinsB.V.), 0.018 g of surfactant Megaface R-40 (from DIC Corporation) in theform of 10% by mass solution in CPN, and 3.86 g of CPN were added, whosesolubilization was visually confirmed, whereby a varnish having a solidcontent of 20% by mass (referred to as SP-21 solution, hereinafter) wasprepared.

The SP-21 solution was spin-coated over a 50 mm×50 mm×0.7 mm thickalkali-free glass substrate with use of a spin coater at 200 rpm for 5seconds, and then at 1,000 rpm for 30 seconds, pre-dried at 80° C. for 3minute on a hot plate, and then irradiated with light of 365 nmwavelength with use of a UV irradiation apparatus at an exposure dose of200 mJ/cm², to obtain a cured film (referred to as SP-21 film,hereinafter).

[Measurement of Solvent Resistance (Crack Resistance) and Transmittance]

The substrate with the cured film formed above was set on a spin coater,and thereon 1 ml of CPN was coated. Next, the cured film was exposed tothe solvent under rotation at 50 rpm for 60 seconds, while preventingthe liquid from being scattered from the substrate. The substrate wasthen rotated at 1,000 rpm for 30 seconds to spin off the solvent. Thesubstrate was finally dried on a hot plate at 80° C. for 10 seconds, andsubjected to measurement of the refractive index, film thickness,calculation of residual film ratio, and observation of the film surfaceunder an optical microscope.

The residual film ratio was estimated by the equation below.

Residual film ratio (%)=[(Film thickness after solvent exposure)/(Filmthickness before solvent exposure)]×100

Also the transmittance was measured before solvent exposure.

Measured results of the refractive index, film thickness, residual filmratio, and average transmittance at 300 to 800 nm are summarized inTable 3, and a micrograph of the surface of the cured film in Example6-1 is shown in FIG. 18 .

TABLE 3 Example 6-1 Before solvent After solvent exposure exposureRefractive index 1.663 1.667 (@550 nm) Thickness 1,640 1.642 (nm)Residual film ratio — 100 (%) Transmittance (%) 91.8 —

Example 6-2

P-23 solution (13.27 g) obtained in Example 5-3, 0.20 g of crosslinkingagent ATM-35E (from Shin Nakamura Chemical Co., Ltd.), 0.20 g ofcrosslinking agent DN-0075 (from Nippon Kayaku Co., Ltd.), 0.12 g ofphotoradical polymerization initiator Omnirad 2959 (from IGM ResinsB.V.), 0.020 g of surfactant Megaface R-40 (from DIC Corporation) in theform of 10% by mass solution in CPN, and 16.19 g of CPN were added,whose solubilization was visually confirmed, whereby a varnish having asolid content of 15% by mass (referred to as SP-22 solution,hereinafter) was prepared.

The SP-22 solution was spin-coated over a 50 mm×50 mm×0.7 mm thickalkali-free glass substrate with use of a spin coater at 200 rpm for 5seconds, and then at 1,000 rpm for 30 seconds, pre-dried at 80° C. for 3minute on a hot plate, and then irradiated with light of 365 nmwavelength with use of a UV irradiation apparatus at an exposure dose of200 mJ/cm², to obtain a cured film (referred to as SP-22 film,hereinafter).

[Measurement of Solvent Resistance (Crack Resistance) and Transmittance]

The substrate with the cured film formed above was set on a spin coater,and thereon 1 ml of CPN was coated. Next, the cured film was exposed tothe solvent under rotation at 50 rpm for 60 seconds, while preventingthe liquid from being scattered from the substrate. The substrate wasthen rotated at 1,000 rpm for 30 seconds to spin off the solvent. Thesubstrate was finally dried on a hot plate at 80° C. for 10 seconds, andsubjected to measurement of the refractive index, film thickness,calculation of residual film ratio, and observation of the film surfaceunder an optical microscope.

The residual film ratio was estimated by the equation below.

Residual film ratio (%)=[(Film thickness after solvent exposure)/(Filmthickness before solvent exposure)]×100

Also the transmittance was measured before solvent exposure.

Measured results of the refractive index, film thickness, residual filmratio, and average transmittance at 300 to 800 nm are summarized inTable 4, and a micrograph of the surface of the cured film in Example6-2 is shown in FIG. 19 .

TABLE 4 Example 6-2 Before solvent After solvent exposure exposureRefractive index 1.628 1.626 (@550 nm) Thickness 889 893 (nm) Residualfilm ratio — 100 (%) Transmittance (%) 92.3 —

1. A triazine ring-containing polymer comprising a repeating unitstructure represented by formula (1) below, having at least one triazinering terminal, and at least a part of the triazine ring terminal beingblocked with an arylamino group having crosslinking group,

wherein each of R and R′ independently represents a hydrogen atom, analkyl group, an alkoxy group, an aryl group, or an aralkyl group, and Arrepresents at least one group selected from those represented by theformulae (2) to (13),

wherein each of R¹ to R⁹² independently represents a hydrogen atom, ahalogen atom, a carboxy group, a sulfo group, an alkyl group having 1 to10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms,or an alkoxy group having 1 to 10 carbon atoms, each of R⁹³ and R⁹⁴represents a hydrogen atom or an alkyl group having 1 to 10 carbonatoms, each of W¹ and W² independently represents a single bond, CR⁹⁵R⁹⁶(each of R⁹⁵ and R⁹⁶ independently represents a hydrogen atom or analkyl group having 1 to 10 carbon atoms (where, they may form a ringtogether)), C═O, O, S, SO, SO₂, or NR⁹⁷ (R⁹⁷ represents a hydrogen atom,an alkyl group having 1 to 10 carbon atoms, or a phenyl group), each ofX¹ and X² independently represents a single bond, an alkylene grouphaving 1 to 10 carbon atoms, or a group represented by formula (14),

wherein each of R⁹⁸ to R¹⁰¹ independently represents a hydrogen atom, ahalogen atom, a carboxy group, a sulfo group, an alkyl group having 1 to10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms,or an alkoxy group having 1 to 10 carbon atoms, and each of Y¹ and Y²independently represents a single bond or an alkylene group having 1 to10 carbon atoms.
 2. The triazine ring-containing polymer according toclaim 1, wherein each of R¹ to R⁹² and R⁹⁸ to R¹⁰¹ independentlyrepresents a hydrogen atom, a halogen atom, or a halogenated alkyl grouphaving 1 to 10 carbon atoms.
 3. The triazine ring-containing polymeraccording to claim 1, wherein the arylamino group having crosslinkinggroup is represented by formula (15),

wherein R¹⁰² represents a crosslinking group.
 4. The triazinering-containing polymer according to claim 3, wherein the arylaminogroup having crosslinking group is represented by formula (16),

wherein R¹⁰² is synonymous as above.
 5. The triazine ring-containingpolymer according to claim 1, wherein the crosslinking group is ahydroxy-containing group or a (meth)acryloyl-containing group.
 6. Thetriazine ring-containing polymer according to claim 5, wherein thecrosslinking group is a hydroxyalkyl group, a (meth)acryloyloxyalkylgroup, or a group represented by formula (i) below,

wherein A¹ represents an alkylene group having 1 to 10 carbon atoms, andA² represents a single bond or a group represented by formula (j) below,

wherein A³ represents a divalent or trivalent aliphatic hydrocarbongroup optionally substituted with hydroxy group, A⁴ represents ahydrogen atom or a methyl group, a represents 1 or 2, and * represents asite of bonding.
 7. The triazine ring-containing polymer according toclaim 6, wherein the crosslinking group is one or more groups selectedfrom hydroxymethyl group, 2-hydroxyethyl group, (meth)acryloyloxymethylgroup, (meth)acryloyloxyethyl group, and groups represented by formulae(i-2) to (i-5) below,

wherein * represents a site of bonding.
 8. The triazine ring-containingpolymer according to claim 1, wherein at least one aromatic ring in Arcontains at least one halogen atom or a halogenated alkyl group having 1to 10 carbon atoms.
 9. The triazine ring-containing polymer according toclaim 1, wherein a part of the triazine ring terminal is further blockedwith a non-substituted arylamino group.
 10. The triazine ring-containingpolymer according to claim 1, wherein the non-substituted arylaminogroup is represented by formula (33).


11. The triazine ring-containing polymer according to claim 1, whereinAr is represented by formula (17).


12. The triazine ring-containing polymer according to claim 1, whereinAr is represented by formula (20).


13. A film-forming composition comprising the triazine ring-containingpolymer according to claim 1, and an organic solvent.
 14. Thefilm-forming composition according to claim 13, wherein the organicsolvent is at least one selected from glycol ester-based solvent,ketone-based solvent, and ester-based solvent.
 15. The film-formingcomposition according to claim 13, further comprising a crosslinkingagent.
 16. The film-forming composition according to claim 15, whereinthe crosslinking agent is a polyfunctional (meth)acrylic compound.
 17. Afilm obtained from the film-forming composition according to claim 13.18. An electronic device comprising a base, and the film according toclaim 17 formed on the base.
 19. An optical component comprising a base,and the film according to claim 17 formed on the base.